CZ43199A3 - Cleansing agent containing enzyme of pectinesterase, detergent admixture and the use thereof - Google Patents

Abstract

The present invention relates to detergent compositions, including dishwashing, hard surface cleaning and laundry compositions containing a pectinesterase substantially free of other pectic enzymes and especially an alkaline pectinesterase for significant overall cleaning performance and stain/soil removal benefits and in particular removal of body, plant, dried-on fruit and vegetables juice soils/stains.

Description

use (57) Annotation:

Detergents are described, including dishwashing detergents, solid surface cleaners and detergents, containing pectinesterase, which does not contain another pectin enzyme, and especially alkaline pectinesterase for their significant overall cleaning effects and anti-dirt/stain properties and especially for their action against body dirt. vegetable dirt, dried fruit and vegetable stains.

Tt/ - C

CLEANING AGENT CONTAINING PECTINESTERASE ENZYME, DETERGENT ADDITIVE AND ITS USE

Field of technology

The invention relates to cleaning agents, including cleaning agents for dishes, cleaning agents for solid surfaces and detergents, containing the pectinesterase enzyme and not containing other pectin enzymes.

Current state of the art

The overall effects of cleaning products used in washing and cleaning, i.e. washing textiles, washing dishes, cleaning solid surfaces, are evaluated by a number of factors, these include the ability of the product to remove applied dirt and stains, the ability of the product to prevent the re-application of dirt or to break down substances arising from the dirt being cleaned objects.

The removal of stains and discolorations originating from plants, wood, mud, clay and fruit is currently the most difficult problem in the field of cleaning agents; especially together with the emerging trend of washing at ever lower temperatures. Such stains usually contain a complex of mixtures of fibrous material based mainly on hydrocarbon compounds and their derivatives: fibrous components and cell wall components. Stains originating from plants are additionally accompanied by amylose, carbohydrates and their derivatives.

It is often very difficult to sufficiently remove food stains from a soiled substrate. A very difficult problem is the removal of strongly colored or "dried dirt" from fruit and/or vegetable juices. Specific examples of such contamination include orange juice, tomato juice, banana, mango or broccoli. Substrates can include textiles, kitchenware or solid surfaces.

Pectin substances are found, for example, in fruit juices. Pectin substances trap suspended particles in these fruit juices, which often become sticky and impermeable in nature. Pectin enzymes are usually used in the food industry in the production of fruit/vegetable juices during juice clarification by breaking down pectin-based substances contained in these juices (depectination).

The benefit of the specific use of pectinesterase enzymes, which do not contain other pectin enzymes in substance, in cleaning formulations, especially for use in laundry, dishwashing and household cleaning work, has not yet been interpreted.

Document DE 36 35 427 is directed to phosphate-free detergents intended for cleaning clothes, containing enzymes with pectinase effects, which, as stated, include such enzymes as polygalacturonase, pectin lyase and/or pectinesterase. However, apart from a general explanation relating to -mixtures of -these- pectinase enzymes for removing inorganic -dirt from clothing, a detailed description relating to an individual pectinase enzyme is found only in Example 3, in which the enzyme (designated as "Enzyme D ”) is characterized by the content of a large amount of pectin lyase. Table III provides the results of the evaluation of this Enzyme D in a cleaning formulation showing that the high-pectin lyase mixture has the highest % pectinase effects (10%) and one of the higher cleaning values (83%) when combined with a high molecular weight water-soluble compound compared to others by said enzymatic means.

The object of the present invention is to provide detergents, cleaning agents intended for washing dishes and household cleaning work, which act against dirt/pollution during their use in washing or cleaning.

In accordance with the present invention, it has now surprisingly been found that pectinesterase enzymes content free from other pectin enzymes, and in particular alkaline pectinesterase content free from other pectin enzymes, provide remarkable effects against a wide range of pollution and stains originating from the body, plants and fruits and increase the actual cleaning profile of cleaning agents.

Of course, the inclusion of the pectinesterase enzyme in a substance not containing other pectin enzymes and especially of the alkaline type ensures particularly enhanced effects in removing body dirt, dried stains/dirt from fruit and vegetable juice.

In addition, the alkaline pectinesterase enzyme, which does not contain other pectic enzymes, has been found to increase the ability and increase the effects of the washing solution, thus providing improved effects of removing body dirt, dirt/stains originating from fruit and vegetable juice, especially when present in very effective washes and cleaning agents. It has also been found that the alkaline enzyme pectinesterase shows a higher tolerance with the base substance of the cleaning agents, for example during the manufacturing process and the storage period.

Furthermore, it has also surprisingly been found that the inclusion of dispersants, especially organic polymeric dispersants, is very beneficial in detergents containing pectinesterase enzymes. Dispersants help disperse the decomposed products of enzymatically decomposed dirt, and thus prevent their re-application on the washed/laundered subjects.

Increased cleaning effects have also been observed when pectinesterase enzymes are combined with another detersive enzyme. Enzymatic bleaching system or the usual activated bleaching system together with pectinesterase enzymes ensures an increased benefit of effects against different stains of different origins.

Furthermore, color stabilizer polymers with anti-staining effects combined with pectinesterase enzymes give enhanced bleaching and/or soil removal effects.

Essential gland

The present invention relates to cleaning agents including dishwashing agents, cleaning agents for solid surfaces and detergents, containing the pectinesterase enzyme and not containing other pectic enzymes, ensuring overall cleaning effects and effects against settled dirt/stains and especially increased effects against body dirt, plant dirt , dried dirt from fruit and vegetable juices.

The preferred composition of the present invention, i.e. the cleaning agent, contains an alkaline pectinesterase enzyme that does not contain other pectic enzymes.

Enzyme pectinesterase

The basic component of the cleaning agents of the invention is the enzyme pectinesterase, which does not contain other pectic enzymes, and especially the alkaline enzyme pectinesterase, which does not contain other pectic enzymes. The term "alkaline" designates a pectinesterase enzyme having enzymatic activity of at least 10%, preferably 25%, more preferably 40% of its optimal activity at a pH ranging from 7 to 11, and includes a pectinesterase having an optimal activity at a pH ranging from 7 to

11. Enzymatic activities are measured by the "Assay of pectinesterase activity" as described by K. Horikoshi in Agr. Biol. Chem., vol 36(2), 286.

The term "pectinesterase" determines the content of EC classification 3.2.1.11.

The term "substantially free of other pectin enzymes" as used herein refers to compositions containing pectinesterase enzyme and containing at most 50% by weight. of pectin enzymes that are not pectin esterase enzymes, preferably less than 25%, more preferably less than 10% and most preferably less than 5% by weight. Such pectin enzymes include, e.g., pectin methylesterases, which hydrolyze pectin methyl ester bonds, and pectin transelimiases or lyases, which act on pectin acids to cause non-hydrolytic cleavage of α-1-4 glycosidic bonds to form unsaturated galacturonic acid derivatives.

The term pectinesterase enzyme used in the text refers to any enzyme that causes the breakdown of pectin substances by splitting ester bonds in pectin forming methanol and dimethylated polygalacturonic acid. Pectin substances can be found in plant tissues and are a common component of fruit juices such as orange, tomato and grapefruit.

Pectinic substances include pectins and pectic acids. Pectins are generally polymers that are formed by chains of galacturonic acids linked by α-1->4 glycosidic bonds.

In natural pectins _, two-thirds of the carboxylic acid groups are usually esterified with methane. Total ester hydrolysis gives pectinic acids.

More, it is assumed without theoretical limitation that higher molecular weight pectin-like materials are present on the textile fibers from the final treatment of the fibers or from subsequent treatments. These higher molecular weight pectin-like materials trap body dirt/stains and their removal increases the effects of removing trapped body dirt/stains from textiles.

A pectinesterase enzyme not containing other pectin enzymes can be prepared by a so-called standard organism or any host organism in which the gene responsible for pectin enzyme production has been cloned and favored.

Pectinesterase enzymes are produced by alkalophilic microorganisms, eg bacterial, fungal and yeast microorganisms such as Bacillus species. Pectinesterase can be produced by Erwinia species. Preferred are E. chrysanthemi, E. carotovora, E. amylovora, E. herbicola, E. dissolvens as described in JP 59066588, JP 63042988 and World J. Microbiol. Microbiotechnol. (8, 2, 115-120), 1992.

Purified pectinesterase can be obtained by purification and/or fractionation of pectin-degrading enzyme mixtures by techniques well known in the art as described by K. Horikoshi in Agr. Biol. Chem., vol 36(2), 288; by V. Shevchik et al. in World Journal of Microbiology and Biotechnology, Vol.8 (1992), 116 and by E. Harris et al., (1989) in "Protein purification methods, practical approach" ”, Ed IRL Press, Oxford, England.

The pectinesterase enzyme is incorporated into the compositions according to the invention preferably at a level of from 0.0001 to 2% by weight, more preferably from 0.0005% to 0.5% by weight, most preferably from 0.001% to 0.1% by weight. of the total amount of pure enzyme.

It is currently common practice to modify standard types of enzymes using protein/genetic engineering techniques to optimize their effectiveness in the detergents of the invention. Variants can be created, for example, so that the compatibility of the enzyme with the usually included admixtures of such agents is increased. Alternatively, a different variant can be prepared so that the optimum pH, bleach stability, catalytic effects and similar enzymatic capabilities are developed precisely for the conditions of the individual cleaning application.

Attention should be primarily focused on oxidation-sensitive amino acids in relation to bleach stability and surface charge relative to surfactant compatibility. The isoelectric point of such enzymes can be modified by the substitution of some charged amino acids, an increase in the isoelectric point can, for example, help to improve compatibility with anionic surfactants. Enzyme stability can be further increased by creating, e.g.

of additional salt bridges and by forcing calcium binding sites to increase the stability of complex-forming chelating agents. ------- - —----------------------- ------------------ --Dispersing agents

It has also surprisingly been found that the incorporation of dispersing agents, especially organic polymeric dispersing agents, is very beneficial in cleaning compositions containing pectinesterase enzymes that do not contain other pectin enzymes, especially alkaline pectinesterase.

Dispersing agents help disperse the decomposed products of enzymatic dirt breakdown, thus preventing their re-application on the washed subjects.

Suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals individually separated by no more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1 596 756. Examples of such salts are polyacrylates of MW (molecular weight) 2000 to 5000 and their copolymers with maleic anhydride, i.e. copolymers having a molecular weight of 1000 to 100,000.

A copolymer of acrylate and methyl acrylate, such as 480N, having a molecular weight of 4,000, can be added particularly advantageously to the cleaning compositions of the present invention at a level of from 0.5 to 20% by weight. means.

The compositions of the invention may contain a lime soap peptizing agent compound that has a lime soap dispersion power (LSDP) as defined below not higher than 8, preferably not higher than 7, most preferably not higher than 6. The lime soap peptizing compound is preferably present in level from 0% to 20% wt.

A numerical measure of the effects of a lime soap peptizing agent is given by the lime soap dispersion power (LSDP), which is determined using the lime soap dispersion test as described in the article ' by H.C. Borghetti and C.A. Bergman, J. Am. Oil. Chem. Soc. (Journal of the American Oil and Chemical Society), vol. 27, pp. 88-90 (1950). This method of lime soap dispersion test is widely used in practice in this field of the current art, reference for example to the content in the following summary articles; W. N. Linfield, Surfactant science Series vol 7, p 3; W. N. Linfield, Tenside surf. det. (Surfactants), Vol 27, pp 159-163 (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, Vol.

104, pp. 71-73 (1989). LSDP is % wt. the ratio of dispersing agent to sodium oleate required to disperse lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water at 333 ppm CaCO ₃ (Ca:Mg=3;2) hardness equivalent.

Surfactants having good lime soap peptizing ability include amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfate compounds, and ethoxylated alcohols (alcohols enriched with ethoxy groups).

with the present invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkylethoxysulfate compounds with an average degree of ethoxylation from 1 to 5, especially C ₁₂ -C ₁₅ alkylethoxysulfate surfactants with a degree of ethoxylation of 3 (LSDP=4) and C ₁₄ - C ₁₅ ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030 individually, from BASF GmbH.

Polymeric lime soap peptizing agents suitable for use according to the invention are described in an article by M.K. Nagarajan, W.F. Masler, and can be found in Cosmetics and Toiletries, Vol. 104, pp. 71-73 (1989).

Hydrophobic bleaching compounds such as 4-[N-octanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-decanoyl-6-aminohexanoyl]benzenesulfonate and mixtures thereof; nonanoyloxybenzenesulfonate together with hydrophilic/hydrophobic bleaching formulations can be used as peptizing compounds of limestone soaps.

Detergent enzymes

Higher effects against a wide range of stains originating from vegetables and fruits can be achieved by combining the pectinesterase enzyme that does not contain other pectin enzymes and especially alkaline pectinesterase with other detergent enzymes.

Synergistic effects are observed in detergents containing the enzyme pectinesterase, which do not contain other pectin enzymes and especially alkaline pectinesterase and cellulase, xylanase and/or protease.

Cellulase enzymes useful for the purposes of the present invention include both bacterial and fungal cellulase species. Advantageously, these types of cellulases will have an optimal pH factor between 5 and 9.5. Suitable types of cellulase enzymes are disclosed in U.S. Pat. Patent 4,435,307, by Barbesgoard et al., in which fungal types of cellulases produced from Humicola insolens are described. Suitable types of cellulases are also disclosed in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2 247 832. Examples of such cellulase enzymes are the types of cellulase produced by the species Humicola insolens (Humicola grisea var. thermoidea), especially Humicola strain DMS 1800. Other suitable types of cellulase include cellulases derived from Humicola insolens having a molecular weight of approximately 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids. Very preferred types of cellulase are cellulases having a benefit in color treatment. Examples of such types of cellulases include the cellulases described in European Patent Application No. 91202879.2, issued November 6, 1991 (Novo).

Carezyme and celluzyme (Novo Nordisk A/S) are very convenient. Also meet sWO

91/17243.

Suitable xylanase enzymes include commercially available types of xylanases such as Pulpzyme HB and

-------5P434 {Novo~Nordiek}rkyxasan (Gist-Brocades),- Optiptílp-a-XyJenase (Solvay).------—

Suitable protease enzymes are subtilisins, which are obtained from certain strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). A particular type of suitable protease is obtained from a strain of Bacillus, which has maximum effects at a pH range of 8 to 12, developed and sold as ESPERASE® by Novo Industries A/S Denmark, hereinafter referred to as "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable types of protease include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEN® (protein driven Maxacal) from International Bio-Synthetics, ln. Netherlands; as well as Proease A disclosed in EP 130 756 A, Jan. 9, 1985 and Protease B disclosed in EP 303 761, Apr. 28, 1987 and EP 130 756 A, Jan. 9, 1985. See also higher pH protease obtained from Bacillus dr. NCIMB 40338 described in WO 93/18140 A by Novo. Enzymatic cleaning compositions comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO 92/03529 A by Novo. Other preferred proteases include those WO 95/10591 A by Procter & Gamble. If desired, a protease having reduced adsorption and increased hydrolysis is available as described in WO 95/07791 by Procter & Gamble. A recombinant type of trypsin-like protease suitable for the cleaning compositions presented by the invention is described in WO 94/25583 by Novo.

In more detail, the protease designated as “Protease D is a carbonyl hydrolase variant with an amino acid sequence not found in nature, which is derived from the carbonyl hydrolase starting material by interchanging different amino acids for the frequency of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76 , preferably also in combination with one or more positions of amino acid residues equivalent to those selected from the group comprising +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, + 128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 in compliance numbering Bcillus amyloliquefaciens subtilisin, as described in WO 95/10591 and in the Patent Application of C. Ghost et al., "Bleaching Compositions Comprising Protease Enzymes", having U.S. Pat. ser. No. 08/322,677, issued October 13, 1994. Also suitable for the purposes of the present invention are the types of proteases described in Patent Application EP 251 446 and WO 91/06637 and the BLAP® protease described in WO 91/02792.

Increased effects of removing body, fruit, vegetable dirt are observed with the cleaning agents of the present invention further containing enzymes that break down starches, sugar and their derivatives, such as amylase, gluco-amylase, dextranase, pullulanase, invertase, laccase, insulinase.

Suitable types of amylases (aa/or β) that can be included in the cleaning compositions of the present invention are: WO 94/02597, Novo Nordisk A/S published February 3, 1994, describing cleaning compositions that include mutant types of amylases. See also WO-947-18314 by-Geneneor—published Aug. 18, 1994;- WO-9-5/40693-©d-Novo Nordisk A/S, published Apr. 20, 1995 and WO 96/02792, by Genencor, published Feb. 22, 1996. Other types of amylases known for use in detergents include both α- and β-amylases. Amylases are known in the art and include the types disclosed in US Patent No. 5,003,257; EP 252 666; WO 91/00353; FR 2,676,456; EP 285 123; EP 525 610; EP 368 341; and British Patent Specification No. 1,296,839 (Novo). Other suitable types of amylase include amylases having increased stability, including Puafact Ox Am ^R described in WO 94/18314, issued August 18, 1994 and amylase variants having an additional modification in the immediately preceding substance available from Novo Nordisk A/S, described in WO 95/ 10603, published April, 1995. Examples of commercial α-amylase products are Termamyl®, Ban®, Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark. WO 95/26397 describes other suitable types of amylases: α-amylases characterized by having specific effects at least 25% higher than the specific effects of Termamyl® in the temperature range of 25°C to 55°C at a pH factor value in the range of 8 to 10, measured by the Phadebas® α-amylase effects test. Other starch-degrading enzymes with improved properties with respect to the level of activity and a combination of heat stability and higher level of activity are described in WO 95/35382.

Other carbohydrases combined with pectinesterase that do not contain other pectin enzymes - especially alkaline pectinesterase - exhibit synergistic effects, such as β-glucanase (lichenase, laminarase) and exo-glucanase (lignase, tannase, pentosanase, malanase and hemi-cellulase).

Finally, the combination of fat and wax hydrolyzing enzymes such as lipase, cutinase and paraphmesterase and pectinesterase enzyme free of other pectin enzymes and especially alkaline pectinesterase ensures synergistic effects of removing stains caused by body, vegetable and fruit impurities.

Suitable lipase enzymes for use in cleaning compositions include enzymes produced by Pseudomonas microorganisms, such as Pseudomonas stutzeri ATCC 19,154, as described in Bristky Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with a lipase antibody produced by Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P “Amano”, hereinafter referred to as “Amano-P”. Other suitable types of lipase commercially available include Amano-CES, lipases from Chromobacter viscosum, e.g. Chromobacter viscosum dr. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipase from U.S. Biochemical Corp., U.S.A.

and Disoynth Co., The Netherlands and lipases from Pseudomonas gladioli. Particularly suitable types of lipases include lipases such as M1 Lipase ^R and Lipomax" (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. - -------------------------------------------- - - — Other suitable ones are cutinases [EC 3.1.1.50], which can be considered a special type of lipase, namely lipases that do not require interfacial activation. The delivery of cutinase enzymes to cleaning compositions has been described in e.g. WO-A-88/09367 (Genencor).

Lipase and/or cutinase enzymes are usually incorporated in the cleaning agent at levels from 0.0001% to 2% by weight. active enzyme cleaner.

The above enzymes may be of any suitable origin, eg plant, animal, bacterial, fungal and yeast. Said enzymes are usually incorporated in the cleaning agent at levels from 0.0001% to 2% by weight. active enzyme cleaner. Enzymes can be supplied as separate separate admixtures (prii! (loose mass), granulates, stabilized liquids, etc. ... containing one enzyme) or as a mixture of two or more enzymes (e.g. joint granulated mass).

Other suitable detergent additives that can be supplied are enzymatic oxidation carriers, which are described in co-pending European Patent Application 92870018.6, issued January 31, 1992. Examples of such enzymatic oxidation carriers are ethoxylated tetraethylene polyamines.

A wide variety of enzymatic materials and means for their incorporation into synthetic detergents are also disclosed in WO 9307263 A and WO 9307260 A by Genencor International, WO 8908694 A by Novo and U.S. Pat. 3,553,139, Jan. 5, 1971 to McOarty et al. Enzymes are further disclosed in U.S. Pat. 4,101,457, to Plač et al., July 18, 1978 and in U.S. Pat. No. 4,507,219, issued to Hughes on March 26, 1985. Enzymatic materials useful for liquid cleaning formulations and their incorporation into such formulations are described in U.S. Pat. Patent 4,261,868, to Hora et al., April 14, 1981. Enzymes used in cleaning compositions can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. Patent 3,600,319, August 17, 1971, to Gedge et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described in, e.g., U.S. Pat. of Patent 3,519,570. A useful Bacillus, species AC13, yielding protease, xylanase and cellulase enzymes is described in WO 9401532 A by Novo.

Bleaching agent

It has been found that the removal of a wide variety of stains/soils originating from plants and/or fruits can be achieved with cleaning compositions containing an enzymatic bleaching system or a conventional activated bleaching system in addition to a pectinesterase enzyme substance not containing other pectin enzymes and especially alkaline pectinesterase.

Bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate with a particle size of 400 to 800

- microns These bleaching agent components may include one or more oxygen bleaching agents and, depending on the bleaching agent selected, one or more bleaching agent activators.

When oxygen bleaching compounds are present, they will typically be present at levels from about 1% to about 25% by weight.

A bleaching agent component suitable for use in the invention may be any bleaching agent useful in cleaning compositions and includes oxygen bleaching agents as well as other bleaching agents known in the art. A bleaching agent suitable for the purposes of the present invention may be an activated or non-activated bleaching agent.

One group of oxygen bleaching agents that can be used includes bleaching agents of percarboxylic acids and their salts. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, magnesium salts of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. U.S. Patent 4,483,781 Patent Application 740,446, European Patent Application 0,133,354 and U.S. Pat. of patent 4,412,934. Very preferred bleaching agents also include acid

6-nonylamino-6-oxoperoxycapron as described in U.S. Pat. Patent 4,634,551.

Another class of bleaching agents that may be used includes halogen bleaching agents. Examples of halogenated bleaching agents include, for example, trichloroisocyanuric acid and the sodium and potassium salts of dichloroisocyanuric acid and N-chloro- and N-bromo-alkanesulfonamides. Such materials are typically supplied at levels of 0.5% to 10% by weight. of the final product, preferably 1% to 5% wt. of the final product.

Hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in U.S. Patent 4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591), or pentaacetylglucose. (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS, described in WO 94/28106), which are perhydrolyzed to form a peracid as an active bleaching agent, leading to improved bleaching effects. Suitable activators are also the acylated citrate esters disclosed in dependent European Patent Application No.

91870207.7.

Useful bleaching agents including peroxyacids, bleaching systems containing bleach activators, and peroxygen bleaching compounds suitable for use in cleaning compositions in accordance with the invention are described in co-pending applications USSN 08/136,626, PCT/US

95/07823, WO 95/27772, WO 95/27773, WO 95/27774 and WO 95/27775.

Hydrogen peroxide can also be incorporated by providing an enzymatic system (ie, an enzyme and therefore a substrate) capable of generating hydrogen peroxide at the start or during washing and/or rinsing. Such enzymatic systems are disclosed in EP Patent Application 91202655.6, filed October 9, 1991. ----------------------------—.....

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persiran, hydrogen peroxide, etc. These are used for "embedded spot bleaching and solution bleaching", i.e. protection against transfer of colors or pigments removed from substrates during washing on other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, such as chloro- and bromo-peroxidase. Cleaning agents containing peroxidase are disclosed, for example, in PCT International Application WO 89/099813, WO 89/09813 and European Patent Application EP No. 91202882.6, filed Nov. 6, 1991 and EP No.

96870013.8, filed Feb. 20, 1996. Another oxidase suitable for inclusion in the cleaning composition of the present invention is iaccase.

Preferred bleach enhancers are 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine substituted with phenothiazine and phenoxazine (described in WO 94/12621), substituted acid salts syringic (salts of syringic acid substituted by C ₃ -C ₅ alkyl) and phenols. Sodium percarbonate and sodium perborate are preferred sources of hydrogen peroxide.

Said peroxidases are usually incorporated in the cleaning agent at levels from 0.0001% to 2% by weight. active enzyme cleaner.

Metal-containing catalysts suitable for use in bleaching compositions include cobalt-containing catalysts such as cobalt pentaamine acetate salts and manganese-containing catalysts of the types described in EPA 549,271; EPA 549,272; EPA 458,397; U.S. Patent 5,246,621; EPA 458,398; U.S. 5,194,416 and U.S. Pat. Patent 5,114,611. A bleaching agent containing a peroxy compound, a bleaching agent catalyst containing manganese and a chelating agent is described in Patent Application No. 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known in the art and may be used in the disclosed compositions. One type of non-oxygen bleaching agent of particular interest includes photoactive bleaching agents, such as sulfonated zinc and/or aluminum phthalocyanines. Said materials can be applied to washed substrates during the washing process. After exposure to light in the presence of oxygen, e.g. by hanging the dried textile in daylight, sulfonated zinc phthalocyanine is activated and the substrate is subsequently bleached. Preferred zinc phthalocyanines and a photoactive bleaching process are described in U.S. Pat. of Patent 4,033,718. Cleaning compositions will typically contain from about 0.025% to about 1.25% by weight. sulfonated zinc phthalocyanine.

Color protectant --------------— ---------------------------- Enhanced bleaching and/ or soil removal has been observed when the detergents of the present invention contain a compound preventing the transfer of colors from one textile to another, i.e. dissolved and suspended colors occurring during the washing of colored laundry.

Polymeric protective agents against staining

The cleaning agents according to the present invention also contain from 0.001% to 10%, preferably from 0.01% to 2%, more preferably from 0.05% to 1% by weight. polymeric anti-staining agents. Said polymeric anti-staining agents are usually incorporated into cleaning agents with the aim of preventing the mutual transfer of colors from the colored textile to the textile simultaneously washed with this agent. These polymers have the ability to complex or adsorb volatile dyes washed from colored textiles before these dyes have a chance to become attached to other articles during washing.

Highly preferred polymeric antistaining agents include polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.

The supply of such polymers also enhances the action of enzymes in accordance with the invention.

a) Polyamine-N-oxide polymers

Post-use polyamine-N-oxide polymers contain units having the following structural formula:

P

AND

And _x

AND

R in which P is a polymerizable unit to which R-N-O may be attached or in which R-N-O may form part thereof or a combination of the two examples may occur.

0 0

II II II

A is NC, CO, C, -0-, -S-;·-Ν«~-)φ-8-r.or -1-;................ ...—— - —-------------R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination of these groups to which the nitrogen of the NO group may be attached or in which is the nitrogen of group N-0 part of this group.

The N-0 group can be represented by the following general structures:

About O

I I (R1)x-N - (R2)y =N-(R1)x (R3)z in which R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x and/or y and/or z is O or 1 and to which the nitrogen of the group N-0 may be attached or in which the nitrogen of the group N-0 is part thereof.

The N-0 group may be part of the polymerizable unit (P) or may be attached to the main chain of the polymer or may be a combination of these two cases.

Suitable polyamine N-oxides in which the N-O group forms part of the polymerizable unit include polyamine N-oxides in which R is selected from the group consisting of aliphatic, aromatic, alicyclic or heterocyclic groups.

A suitable class of said polyamine-N-oxides includes the group of polyamine-N-oxides in which the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and their derivatives.

Other polyamine-N-oxides mentioned here include a group of polyamine-N-oxides in which the nitrogen of the NO group is attached to the R group.

Other suitable polyamine N-oxides are polyamine oxides in which the N-O group is attached to a polymerizable unit.

A preferred class of these polyamine N-oxides are polyamine N-oxides having the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O functional group is part of said R group.

Examples of these classes are polyamine oxides, where R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives.

Another preferred class of polyamine N-oxides includes polyamine oxides having the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group in which the nitrogen of the N-O functional group is attached to said R groups.

Examples of such classes include polyamine oxides in which the R groups may be aromatic, such as phenyl.

Any polymer backbone can be used as long as the amine oxide polymer formed is water soluble and has anti-staining and color transfer properties. Examples of suitable polymer backbones are polyvinyls, polyalkenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof.

The amine-N-oxide polymers of the present invention have an amine to amine-N-oxide ratio of 10:1 to 1:1,000,000. The amount of amine oxide groups present in the polyamine oxide polymer may, however, vary according to the appropriate copolymerization or the appropriate degree of N-oxidation. A preferred ratio of amine to amine N-oxide is from 2:3 to 1:1,000,000. More preferably from 1:4 to 1:1,000,000, most preferably from 1:7 to 1:1,000,000. Polymers of the present invention currently include irregular or block copolymers in which one type of monomer is an amine-N-oxide and the other type of monomer is either an amine-N-oxide or not. The amine oxide unit of polyamine N-oxides has a PKa < 10, preferably a PKa < 7, more preferably a PKa < 6.

Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical provided that the material has the required water solubility and color stability.

The average molecular weight is usually in the range of 500 to 1,000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

The N-vinylimidazole-N-vinylpyrrolidone polymers used in the present invention have an average molecular weight ranging from 5,000 to 1,000,000, preferably from 5,000 to 200,000.

Very preferred polymers suitable for use in cleaning compositions in accordance with the invention include a polymer selected from N-vinylimidazole - N-vinylpyrrolidonone copolymers, wherein said polymer has an average molecular weight in the range of from 5,000 to 50,000, more preferably from 8,000 to 30,000 , most preferably from 10,000 to 20,000.

The average molecular weight range was determined by light scattering according to the vBarth description

H. G. and Mays J.W., Chemical Analysis, Volume 113, "Modern Methods of Polymer Characterization".

All preferred N-vinylimidazole-^¼4rϊy^pyτr©lid&n©vé--k©pβ{ym&Fy-maj^~prt^fflěfROtí-flfŤ®te^w}ary weight in the range from 5,000 to 50,000; more preferably from 8,000 to 30,000; preferably from 10,000 to 20,000.

N-vinylimidazole - N-vinylpyrrolidone copolymers, characterized by having an average molecular weight in the specified range, ensure excellent color stabilization properties, while not having an adverse effect on the cleaning effects of formulated cleaning agents containing this substance. The N-vinylimidazole - Nvinylpyrrolidone copolymer of the present invention has a N-vinylimidazole to N-vinylpyrrolidone molar ratio of from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.

c) Polyvinylpyrrolidone

The cleaning compositions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5 000 to about 15,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trade names PVP K-15 (viscometrically determined molecular weight 10,000), PVP K-30 (average molecular weight 40,000) , PVP K-60 (average molecular weight 160,000) and PVP K-90 (average molecular weight 360,000). Other suitable polyvinylpyrrolidones that are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to those skilled in the field of cleaning agents (see e.g. EP-A-262 897 and EP-A-256 696).

d) Polyvinyl oxazolidone

The cleaning compositions of the present invention may also utilize polyvinyl oxazolidone as a polymeric anti-staining stabilizer. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, most preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

e) Polyvinylimidazole ciotieí—means- -presented -invention—m-shotí-Haká—use—polyvinyltriridazole· i@ko-— a polymeric fixing agent acting against staining. Said polyvinylimidazoles have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5

000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.

f) Cross-linked polymers

Cross-linked polymers represent polymers whose main chains are interconnected in a certain order; these bonds can be chemical or physical in nature, active groups on the main chain or on branches are also possible; cross-linked polymers were reported in the Journal of Polymer Science, Volume 22, pp. 1035-1039.

According to one formulation, the cross-linked polymers are prepared in such a way that they form a three-dimensional solid structure that can trap dyes in the pores formed by the three-dimensional structure. According to another formulation, cross-linked polymers capture dyes by swelling.

Such crosslinked polymers are described in a pending patent application

94870213.9.

Detergent additives

The cleaning agents of the invention may also contain additional detergent additives. The exact nature of these additional ingredients and the level of their incorporation will depend on the physical form of the composition and the nature of the cleaning for which the composition is to be used.

The cleaning agents according to the invention can be liquid agents, pastes, gels, sticks, tablets, bulk or granular material. Granular agents can also be in "condensed" form, liquid agents can also be in "concentrated" form.

Agents according to the invention can be formulated, for example, as agents intended for hand washing dishes or for automatic dishwashers, agents for hand washing or washing in an automatic washing machine including detergent additives and agents suitable for use in soaking and/or pre-washing soiled textiles, fabric softeners supplied during rinsing and means intended for usual household cleaning work.

Said compositions containing pectinesterase can be used in the washing of textiles, for stain removal, bleaching, softening, adjustment of color brightness and color stabilization, if they are formulated in detergents.

Means according to the invention, if hand-washed, preferably contain a surface-active substance and preferably another cleaning compound selected from the group including organic polymer compounds, foaming agent, group II metal ions, solvents, hydrotropic substances and accessory enzymes.

The compositions of the invention, if they are formulated as compositions suitable for use in automatic washing machines, usually contain both a surface-active substance and a filler compound and additionally one or more detergent components preferably selected from the group including organic polymer compounds, bleaching agents, additional enzymes, saponification suppressors dispersed agents, dispersing agents for lime soaps, suspensions acting against dirt and agents acting against its recapture, corrosion inhibitors. Detergents may also contain fabric softeners as additional detergent components.

The compositions of the invention can also be used as detergent supplement products. Such additional products are intended to complement or support the effects of conventional cleaning agents.

The density of the laundry detergents according to the invention ranges from 400 to 1200 g/liter, preferably from 600 to 950 g/liter of the product, measured at a temperature of 20°C.

The "thickened" form of the compositions according to the invention is best expressed by the density and, in terms of the composition, by the amount of inorganic salts of the fillers; inorganic salts of fillers are usual admixtures of cleaning agents in loose form; salts of fillers are present in usual cleaning agents in a content amount of usually 17% to 35% by weight. of the total resource.

The thickened compositions contain the salt of the filler in amounts not exceeding 15% of the total composition, the amount preferably not exceeding 10% by weight, most preferably not exceeding 5% by weight. means.

The inorganic salts of the fillers intended for use in the presented compositions are selected from the group including alkali salts and alkaline earth metal salts, e.g. sulfates and chlorides.

A preferred filler salt is sodium sulfate.

Liquid cleaning agents according to the invention may also have a "concentrated form", in which case the liquid cleaning agents according to the present invention will contain a lower amount of water compared to conventional liquid cleaning agents.

The water content of the concentrated liquid detergent is usually preferably lower than 40%, more preferably lower than 30%, most preferably lower than 20% by weight. cleaning agent.

Surfactant system

-Detergents in accordance with the -^presented- invention-containing-system-of-surface-active----substances, in which the surface-active substances can be selected from the group including non-ionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or semipolar surfactants.

Surfactant is usually present at a level of from 0.1% to 60% by weight. More preferred levels of incorporation are in the range from 1% to 35% by weight, most preferably from 1% to 30% by weight. cleaning agents in accordance with the invention.

The surfactant is preferably formulated in a form compatible with the enzymatic components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to promote or at least not reduce the stability of any enzyme in such compositions.

A preferred surfactant system for use in accordance with the present invention comprises one or more nonionic and/or anionic surfactants described below as a surfactant.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkylphenols are suitable as the nonionic surfactant of the surfactant system of the present invention, polyethylene oxide condensates are more preferred. Such compounds include condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in a straight or branched chain configuration with an alkene oxide. In a preferred composition, ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles of ethylene oxide per mole of alkylphenols. Commercially available nonionic surfactants of this type include Igepal™ CO-630, sold by GAF Corporation: and Triton™ X45, X-114, X-100, and X-102, all sold by Rohm & Haas Company. These surfactants are usually referred to in context as alkylphenol alkoxylates (alkylphenols with introduced alkoxy groups) (eg alkylphenol ethoxylates (alkylphenols having introduced ethoxy groups)).

Condensation products of primary and secondary aliphatic alcohols containing from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The alkyl chain of an aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms and containing from about 2 to about 10 moles of ethylene oxide per mole of alcohol are preferred. Amounts of from about 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles are present in said condensation products

-------ethylene oxide on-mono-mol!-alcohol. Examples Commercially available p,©ionic surfactant kits of this type include Tergitol™ 15-S-9 (condensation product of a C^-C^ linear alcohol with 9 moles of ethylene oxide), Tergitol™ 24-L-6 NMW (condensation product C ₁₂ -Ci ₄ primary alcohol with 6 moles of ethylene oxide with a tight molecular weight distribution), both sold by Union Carbide Corporation: Neodol™ 45-9 (condensation product of a C ₁₄ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol™ 23 -3 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 3.0 moles of ethylene oxide), Neodol™ 45-7 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 7 moles of ethylene oxide), Neodol™ 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide) sold by Shell Chemical Company, Kyro™ EOB (condensation product of C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide sold by The Procter & Gamble Company and Genapol LA 030 or 050 (condensation product of C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide) sold by Hoechst. The preferred HLB equilibrium range of these products is from 8 to 11 and most preferably from 8 to 10.

Alkylpolysaccharides disclosed in the U.S. of Patent 4,565,647, Llenado, filed January 21, 1986 having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and polysaccharides, e.g., polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 carbohydrate units are also useful as the nonionic surfactant of the surfactant systems of the present invention. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. glucose, galactose and galactosyl moieties can be exchanged for glucosyl moieties (optionally a hydrophobic group is attached at the 2-, 3-, 4-, etc. position, thus giving glucose or galactose as opposed to glucoside or galactoside). The internal saccharide linkages can be, for example, between one position of the additional saccharide units and the 2-, 3-, 4- and/or 6-positions of the preceding saccharide units.

Preferred alkyl polyglycosides have the formula

R^CnHznOMglycosyl), in which R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms; n is 2 or 3, more preferably 2; t takes on values from approximately 0 to 10, preferably 0; x takes on values from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxyalcohol is first prepared, which is then subjected to a reaction with glucose or a source of glucose to form a glucoside (attachment to the l-positionL-Additional glycosyl units can-be-subsequently-attached between their 1-position and 2-, 3-, 4- and/or 6-positions of the preceding glycosyl units, preferably mainly the 2-position.

Condensation products of ethylene oxide with a hydrophobic base prepared by condensation of propylene oxide with propylene glycol are also suitable for use as complementary nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will appear to be insoluble in water. The addition of polyoxyethylene parts to this hydrophobic portion leads to an increase in water solubility of the molecule as a whole, while the liquid nature of the product is maintained up to the point where the polyoxyethylene content is approximately 50% of the total weight of the condensation product, which corresponds to condensation with approximately up to 40 moles of ethylene oxide. Examples of compounds of this type include certain types of Plurafac™ LF404 and Pluronic™ surfactants available commercially and sold by BASF.

Condensation products of ethylene oxide with the product obtained from the reaction of propylene oxide and ethylenediamine are also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The hydrophobic portion of these products contains the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight. polyoxyethylene and had a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain types of Tetronic™ compounds commercially available and sold by BASF.

Polyethylene oxide condensates of alkylphenols, condensation products of primary and secondary aliphatic alcohols containing from about 1 to about 25 moles of ethylene oxide, alkyl polysaccharides and mixtures thereof are also suitable for use as a nonionic surfactant in a surfactant system. The most preferred are C8-C14 alkylphenol ethoxylates having from 3 to 18 ethoxy groups and C8- _{C18 alcohol} ethoxylates (preferably _C10 average) having from 2 to 10 ethoxy groups and mixtures thereof.

Very preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

R ² - C - Ν - Z II I

..............O..... R ¹ ...........- -· ------------in which R ¹ is hydrogen, or R ¹ is C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R ² is C 5 -C ₃₁ hydrocarbyl, and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain or their alkylated derivatives. Preferably R ¹ is methyl, R ² is a straight C _n -C ₁₅ alkyl or C ₁₆ -C ₁₈ alkyl or alkenyl chain such as coconut oil alkyl or mixtures thereof and Z is derived from a reducing sugar such as glucose, fructose, maltose , lactose, during the reductive amination reaction.

Anionic surfactants suitable for use include linear alkyl benzene sulfonates, alkyl ester sulfonate surfactants, including linear C ₈ -C 20 carboxylic acid esters (ie, fatty acids) that are sulfonated with SO ₃ gas in accordance with "The Journal of the American Oil Chemists Society (Journal of the American Chemical Oil Society)' 52 (1975), pp. 323-329. Suitable starting materials will include natural fatty substances derived from tallow, palm oil, etc.

Suitable alkyl ester sulfonate surfactants, especially for washing, include alkyl ester sulfonate surfactants of the structural formula:

O

II

R ³ - CH - C - OR ⁴ I so ₃ m in which R ³ is C8-C20 hydrocarbyl, preferably alkyl or a combination thereof, R ⁴ is CrC ₆ hydrocarbyl, preferably alkyl or a combination thereof and M is a cation that completes the soluble salt in water with alkyl ester sulfonate. Suitable water-soluble cations include metals such as sodium, potassium and lithium and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Very preferred are methyl ester sulfonates in which R ³ is C 1 -C 10 alkyl.

Other suitable anionic surfactants include alkyl sulfate surfactants which are water soluble salts or acids of the formula ROSO ₃ M wherein R is preferably

C ₁₀ -C ₂ 4 hydrocarbyl, preferably alkyl or hydroxyalkyl having a C ₁₀ -C 20 alkyl component, more preferably

C ₁₂ -C ₁₈ alkyl or hydroxyalkyl and M is hydrogen or a cation, e.g. an alkali metal cation (e.g.

sodium, potassium, lithium) or ammonium or substituted ammonium (e.g. methyl-, dimethyl- and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethylammonium and ^J -------dimethylpiperidiniwn cations and quaternary ar^n -cations-removed-p-alkylamines, such as ethylamine, diethylamine, triethylamine, their mixtures and the like).

C ₁₂ .C ₁₆ alkyl chains are usually preferred for lower wash temperatures (e.g. temperature below 50°C) and C ₁₈ -C ₁₈ alkyl chains are preferred for higher wash temperatures (e.g. temperatures above approximately 50°C). Other anionic surfactants useful for detersive purposes may also be included in the cleaning compositions of the present invention. These agents may include salts including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) soaps , C ₈ -C _{2 2} primary or secondary alkanesulfonates, C ₈ -C ₂ 4 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g. as described in British Patent Application No. 1,082,179, C ₈ C ₂ 4 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates, such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂ -Ci ₈ monoesters) and sulfosuccinate diesters (especially saturated and unsaturated C ₈ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglucoside sulfates (nonionic non-sulfated compounds, which are described later in the text), branched primary alkyl sulfates and alkyl polyethoxycarboxylates having the formula RO(CH ₂ CH ₂ O) _to CH ₂ COO-M ⁺ , in which R is C ₈ -C 22 alkyl, k is an integer from 1 to 10, and M is a cation forming a water-soluble salt. Resin acids and hydrogenated resin acids are also suitable, such as resins, hydrogenated resins and resin acids and hydrogenated resin acids present in or obtained from tall oil.

Additional examples are described in Surface Active Agents and Detergents Volumes I and II by Schwartz, Perry and Berch. Various surfactants of this type are also generally disclosed in U.S. Pat. of Patent 3,929,678, issued Dec. 30, 1975 to Laughlin et al., column 23, line 58 to column 29, line 23 (indicated by notes in the text).

Laundry detergents of the present invention typically contain, if included, from about 1% to about 40% by weight, preferably from about 3% to about 20% by weight. of such anionic surfactants.

Highly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants, which are water-soluble salts or acids of the formula RO(A) _m SO ₃ R, wherein R is an unsubstituted C ₁₀ -C ₂ 4 alkyl or hydroxyalkyl group having C ₁₀ - C ₂ 4 alkyl moiety, preferably C ₁₂ C 20 alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is I ethoxy or propoxy unit, m is greater than zero, usually ranging from about 0.5 to about I to 6 , more preferably in the range of from about 0.5 to about 3, and M is hydrogen or a cation, which I may be a non-metal cation (e.g. sodium, potassium, lithium, calcium magnesium, etc.), ammonium or ------ I substituted ammonium cations. Alkyl ethoxy sulfates as well as alkyl propoxy sulfates are also contemplated for the purposes of the invention. Specific examples of substituted ammonium cations I include methyl-, dimethyl-, trimethyl-ammonium cations, and quaternary ammonium cations, such as I tetramethylammonium and dimethylpiperidinium cations, and types derived from alkylamines, such I as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Examples of surfactants include C ₁₂ -C ₁₈ alkyl polyethoxy (1.0) sulfate (C ₂ -C ₁₈ E(1.0)M), C ₁₂ -C ₁₈ alkyl polyethoxy (2.25) I sulfate (C ₁₂ - Ci ₈ E(2,25)M), C ₁₂ -C ₁₈ alkylpolyethoxy (3,0) sulfate (C ₁₂ -C ₁₈ E(3,0)M) and C-, ₂ -C ₁₈ I alkylpolyethoxy (4, 0) sulfate (C ₁₂ -C ₁₈ E(4,0)M), in which M is usually selected from group I comprising sodium and potassium. AND

The cleaning agents of the present invention may also contain cationic, ampholytic, zwitterionic and semipolar surfactants, as well as nonionic and/or anionic surfactants, other than those already described above in the text.

Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention have one long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethylammonium halides and surfactants having the formula:

[R ² (OR ³ )y] [R ⁴ (OR ³ )y] ₂ R ⁵ N ⁺ X' in which R ² is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, the individual R ³ are selected from the group consisting of -CH2CH2-, CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2- and mixtures thereof; each R ⁴ is selected from the group consisting of CrC ₄ alkyl, CTC 4 hydroxyalkyl, benzyl ring structures formed by joining two R ⁴ groups, -CH 2 CHOH-CHOHCOR ⁶ CHOHCH 2 OH, wherein R ⁶ is any hexose or hexose polymer having a molecular weight of less than about 1000, and hydrogen if y is not 0; R ⁵ j is the same as R ⁴ or represents an alkyl chain of which the total number of carbon atoms of R ² plus R ⁵ is not greater than about 18; the individual y's range from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.

A quaternary ammonium surfactant suitable for use in the present invention has the formula (I): j

R ’^Ο

(O in which R·, is alkyl (C ₆ -C ₁₀ ) having a short chain length or alkylamidoalkyl of formula (II):

(II) where y is 2 to 4, preferably 3, where R ₂ is hydrogen or C 1 -C ₃ alkyl, where x is 0 to 4 preferably 0 to 2, most preferably 0, where R ₃ , R ₄ and R ₅ are either the same or different and may contain both a short alkyl chain (CrC ₃ ) or an alkoxylated alkyl of formula III, where Χ' is the opposite ion, preferably a halide, e.g. chloride or methyl sulfate.

(III) in which R ₆ is C _r C ₄ and z is 1 or 2.

Preferred quaternary ammonium surfactants are those defined in formula I wherein

R-ι is C _Sr C-to or its Gb mixture, x=0, - -· — ------—......... —

R ₃ , R ₄ = CH ₃ and R ₅ = CH ₂ CH ₂ OH.

Very preferred cationic surfactants are water-soluble quaternary ammonium compounds usable in the above compositions having the formula

RiR ₂ R ₃ R ₄ N ⁺ X' (i) in which R-ι is C ₈ -C ₁₆ alkyl, individual R ₂ , R ₃ and R ₄ independently represent C _r C ₄ alkyl, CrC ₄ hydroxyalkyl and -(C ₂ H ₄₀ )xH in which x has a value from 0 to 5 and X is an anion. No more than one of R ₂ , R ₃ or R ₄ should be benzyl. The preferred alkyl chain length for Ri is Ci ₂ -Ci ₅ , especially when the alkyl group is a mixture of chain lengths derived from coconut oil or palm kernel oil or is obtained synthetically by olefin formation or OXO synthesis of alcohols. Preferred groups R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups, and the anion X may be selected from the group consisting of halide, methosulfate, acetate and phosphate ions.

Examples of preferred quaternary ammonium compounds of formula (I) for the purposes of the invention are; trimethylammonium chloride or bromide of coconut oil; coconut oil methyldihydroxyammonium chloride or bromide; decyltriethylammonium chloride;

decyldimethylhydroxyethylammonium chloride or bromide;

C ₁₂ C ₁₅ dimethylhydroxyethylammonium chloride or bromide; dimethylhydroxyethylammonium- chloride or bromide of coconut oil; myristyl trimethylammonium methyl sulfate;

lauryldimethylbenzylammonium chloride or bromide; lauryldimethyl(ethenoxy) ₄ ammonium chloride or bromide;

... cholinesters (compounds of formula (I) in which R is CH 2 -CH 2 -OCC ₁₂ . ₁₄ alkyl II and R ₂ , R ₃ and R ₄ represent methyl);

di-alkylimidazoles (compounds of formula (I)).

Other cationic surfactants useful for the purposes of the invention are also described in U.S. Pat. Patent 4,228,044, Cambre, issued October 14, 1980 and in European Patent Application EP 000 224.

Common cationic softening agents include softening quaternary ammonium actives insoluble in water, the most commonly used being alkyl ammonium chloride or double alkyl methyl sulfate.

Preferred cationic softening agents of this type include the following:

1) tallow dimethylammonium chloride (DTDMAC);

2) tallow dihydrogenated dimethylammonium chloride;

3) tallow dihydrogenated dimethylammonium methyl sulfate;

4) distearyldimethylammonium chloride;

5) dioleyldimethylammonium chloride;

6) dipalmitylhydroxyethylmethylammonium chloride;

7) stearylbenzyldimethylammonium chloride;

8) tallow trimethylammonium chloride;

9) hydrogenated tallow trimethylammonium chloride;

10) C ₁₂ -14 alkyl hydroxyethyldimethylammonium chloride;

11) C ₁₂ .18 alkyldihydroxyethylmethylammonium chloride;

12) di(stearoyloxyethyl)dimethylammonium chloride (DSOEDMAC);

13) di(oxy-alkyl tallow ethyl)dimethylammonium chloride;

14) di-tallow imidazolinium methylsiran;

15) 1-(2-alkyl tallow-amidoethyl)-(di-alkyl tallow)-imidazolinium methyl sulfate.

Biodegradable quaternary ammonium compounds have been introduced as alternatives to the commonly used double alkyl chain ammonium chlorides and methyl sulfates. Such quaternary ammonium compounds contain alkyl(en)yl groups having long chains interrupted by functional groups such as carboxy groups. Said materials and fabric softening agents with their content are described in a number of publications, such as EP-A-0 040 562 and EP-A-0 239 910.

Quaternary ammonium compounds and amine starting materials suitable for the purposes of the invention have the formula (I) or (II) as follows:

R? _x R2 * (CH-vO-r'

Rl

X'

R3

- N— (CH ₂ ) _n -CH -CH 1

R3 - Q (J

II ýi Ť* in which Q is selected from the group consisting of -OC(O)-, -C(O)-O-, -OC(O)-O-, -NR ⁴ -C(O)-, -C( O)NR ⁴ -;

R ¹ is (CH ₂ ) _n -QT ² or T ³ ;

R ² is (CH ₂ ) _m -QT ⁴ or T ⁵ or R ³ ;

R ³ is C _{1 -C 4} alkyl or C 1 -C ₄ hydroxyalkyl or hydrogen;

R ⁴ is hydrogen or C _{1 -C 4} alkyl or C _{1 -C 4} hydroxyalkyl;

T ¹ , T ² , T ³ , T ⁴ , T ⁵ independently represent Cn-Cz? alkyl or alkenyl;

n and m are integers from 1 to 4; and

X' is a softening compatible anion.

Non-limiting examples of compatible anions in the softening agent include chloride or methyl sulfate.

The alkyl or alkenyl chain T ¹ , T ² , T ³ , T ⁴ , T ⁵ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chain can be straight or branched.

Tallow is a common and inexpensive source of long chain alkyl and alkenyl material. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of materials having long chains typical of tallow are very preferred.

Specific examples of quaternary ammonium compounds suitable for use in the aqueous softening compositions of the invention include.

1) N,N-di(alkyl tallow-oxyethyl)-N,N-dimethylammonium chloride;

2) N,N-di(alkyl tallow-oxy-ethyl)-N-methyl-N.(2-hydroxyethyl)ammonium methyl sulfate;

3) N,N-di(2-alkyl tallow-oxy-2-oxo-ethyl)-N,N-dimethylammonium chloride;

4) N,N-di(2-alkyl tallow-oxy-ethylcarbonyl.oxy-ethyl)-N,N-dimethylammonium chloride;

5) N-(2-alkyl tallow-oxy-2-ethyl)-N-(2-alkyl tallow-oxy-2-oxo-ethyl)-N,Ndimethylammonium chloride;

6) N,N,N-tri(alkyl tallow-oxy-ethyl)-N-methylammonium chloride;

7) N-(2-alkyl tallow-oxy-2-oxoethyl)-N-(alkyl tallow-N,N-dimethyl)ammonium chloride; and

8) 1,2-di-alkyl tallow-oxy-3-trimethylammoniopropane chloride;

and mixtures thereof of any of the above materials.

The cleaning compositions of the present invention typically contain, if included, from about 0.2% to about 25% by weight, preferably from about 1% to about 8% by weight. of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the cleaning agents of the present invention. Such surfactants may be broadly described as aliphatic derivatives of secondary and tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical may be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, usually from about 8 to about 18 carbon atoms, and at least one contains a water-soluble anionic group, eg, carboxy, sulfonate, sulfate. Meet the U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, lines 18 to 35, eg, ampholytic surfactants.

The cleaning compositions of the present invention typically contain, if included, from about 0.2% to about 15% by weight, preferably from about 1% to about 10% by weight. of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in cleaning agents. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium compounds, quaternary phosphonium compounds and tertiary sulfonium compounds. Meet the U.S. Patent No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975, column 19, line 38 to column 22, line 48, eg with zwitterionic surfactants.

The cleaning compositions of the present invention will typically contain, if included, from about 0.2% to about 15% by weight, preferably from about 1% to about 10% by weight. of this zwitterionic surfactant.

Semipolar nonionic surfactants are a special class of nonionic surfactants that include water-soluble amine oxides containing one alkyl moiety having from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having from about 1 to about o 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety having from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups having from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety having from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms.

Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula;

O

T

R ³ (OR ⁴ ) xN (R ⁵ ) 2 wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group or a mixture thereof containing from about 8 to about 22 carbon atoms; R ⁴ is an alkene or hydroxyalkene group containing from approximately 2 to approximately 3 carbon atoms or a mixture thereof; x is a value from 0 to approximately 3; and each R ⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. R ⁵ groups can be connected to each other, e.g. through an oxygen or nitrogen atom, creating a ring structure.

These amine oxide surfactants mainly include C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

The cleaning agents of the present invention usually contain, experiments are included, from about 0.2% to about 15% by weight, preferably from about 1% to about 10% by weight. teak semipolar nonionic surfactants.

The cleaning agent according to the present invention may further contain an additional "common" surfactant selected from the group comprising primary or tertiary amines.

Suitable primary amines for the purposes of the invention include amines according to the formula RiNH ₂ in which RJe is C ₆ -Ci 2 . preferably a C ₆ -C ₁₀ alkyl chain or R ₄ X(CH ₂ ) _n , X is -O-, -C(O)NH- or NH-, R ₄ is a C ₆ -Ci 2 alkyl chain, n is in the range of 1 to 5, preferably 3. The R 1 alkyl chain may be straight or branched and may be interrupted by up to 12, preferably less than 5 ethylene oxide moieties.

Suitable amines of the above formula include n-alkylamines. Suitable amines for use in the invention may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Tertiary amines suitable for use in the invention include tertiary amines having the formula R ₁ R ₂ R ₃ N in which R ₁ and R ₂ are C 1 -C ₈ alkyl chains or

_R5

I — (CH ₂ — CH — O) _x H

R ₃ is either C ₆ -C 12 , preferably a C ₆ -C ₁₀ alkyl chain or R ₃ is R^CH^n in which X is -O-, C(O)NH- or -NH-, R ₄ is C ₄ -C ₁₂ , n is in the range from 1 to 5, preferably 2 to 3. R ₅ is hydrogen or C _r C ₂ alkyl and x is in the range from 6 to 6.

R ₃ and R ₄ may be linear or branched; preferably less than 5 ethylene oxide parts.

Preferred tertiary amines are R ₁ R ₂ R ₃ N , in which R 1 is a C ₆ -C ₁₂ alkyl chain, R ₂ and R ₃ are C _r C ₃ alkyl or

Rs — ( CH ₂ CH — O ) _x H in which R ₅ is hydrogen or CH ₃ and x = 1 to 2.

Amidoamines of the formula are also preferred

O

II

R 1 — C — NH — (CH ₂ ) _n — N —-(R ₂ ) ₂ in which R 1 is C ₆ -C ₁₂ alkyl; n is 2 to 4, preferably n is 3; R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1dodecylamine, C ₈ -C ₁₀ oxypropylamine, N-coco-1-3 diaminopropane (coco = coconut oil alkyl), cocoalkyldimethylamine, lauryldimethylamine, laurylbis(hydroxyethyl) amine, cocobis(hydroxyethyl)amine, laurylamine propoxylated 2 moles, octylamine propoxylated 2 moles, amidopropyldimethylamine, C ₈ -C ₁₀ amidopropyldimethylamine and C ₁₀ amidopropyldimethylamine. The most preferred amines suitable for use in the compositions of the invention are 1-hexylamine, 1-octylamine,

1-decylamine, 1-dodecylamine. Very desirable are n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and oleylamine 7 times ethoxylated, laurylamidopropylamine and cocoamidopropylamine.

Benefit in treating the color of the substrate

Color fastness technology and other types of color treatments may also be included. Examples of these technologies are metal catalysts intended for the treatment of color quality. These metal catalysts are described in the jointly pending European Patent Application No. 92870181.2.

Filler system

-------Pretraces in accordance-with-the-present-invention can further contain-h&^ic fillerr-Any suitable system of fillers is suitable for use for the purposes of the invention including alumino-silicate materials, silicate, polycarboxylates, alkyl- or alkenyl succinic acid and fatty acids, materials such as ethylenediaminetetraacetate, diethylenetriaminepentamethyleneacetate, metal ion complexing agents such as aminopolyphosphates, especially ethylenediaminetetramethylenephosphonic acids and diethylenetriaminepentamethylenephosphonic acid. Phosphate fillers may also be used at this location.

Suitable fillers may be inorganic ion exchange materials, usually an inorganic hydrated aluminate material, more preferably a hydrated synthetic zeolite, such as hydrated zeolite A, X, B, HS or MAP.

Another suitable inorganic filler material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate containing sodium silicate (Na ₂ SÍ2O ₅ ). Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and their ether derivatives, as described in Belgian Patent Nos. 831 368, 821 369 and 821 370. Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy(diacetic), maleic, diglycolic, tartaric, tartaric, and fumaric acids, as well as the ether carboxylates described in German Patent Applications 2,446,686 and 2,446,687 and US Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Pat. No. 840 623. Also useful are polycarboxylates containing three carboxyl groups, in particular the water-soluble salts of citrates, the salts of aconitic acid and the water-soluble salts of citraconic acid, as well as derivatives of succinates, such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in Dutch Application 7205873 and oxypolycarboxylate materials such as 2-oxa1,1,3-propanetricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include the oxydiasuccinates described in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat. Patent No. 3,936,448 and sulfonated pyrolyzed citrates disclosed in British Patent No. 1,082,179, while polycarboxylates containing phosphonium substituents are disclosed in British Patent No. 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-c/s, cis, c /s-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran-c/s, cis, c/s-tetracarboxylates, 2,5tetrahydrofuran-c/s-dicarboxylates, 2,2,5,5-terahydrofuran-tetracarboxylates , 1 “3,4,5,6-hexane32 hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and derivatives of violet acid disclosed in British Patent Application No. 1,425,343.

.... Preferred polycarboxyphate groups from the above are hydF9-xycarboxylates containing up to three carboxyl groups per molecule, more specifically citrates.

Preferred filler systems suitable for use in the present compositions include mixtures of a water-insoluble aluminosilicate filler such as zeolite A or layered silicate (SKS-6) and a water-soluble carboxylate chelating agent such as citric acid. Preferred filler systems suitable for use in the liquid compositions of the present invention are soaps and polycarboxylates.

A chelating agent suitable for inclusion in cleaning compositions according to the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof or mixtures thereof. Suitable EDDS compounds are the free acid forms and their sodium or magnesium salts. Examples of preferred sodium salts of EDDS include Na ₂ EDDS and Na ₄ EDDS. Examples of preferred magnesium salts of EDDS include MgEDDS and Mg ₂ EDDS. Magnesium salts are most preferred for inclusion in compositions in accordance with the invention. Preferred filler systems include a mixture of a water-insoluble aluminosilicate filler such as Eolite A and a water-soluble carboxylate chelating agent such as citric acid.

Other filler materials that may form part of a filler system suitable for use in granular compositions include inorganic materials such as carbonates, acid carbonates and alkali metal silicates and organic materials such as organic phosphorites, aminopolyalkene phosphorites and aminopolycarboxylates.

Other suitable water-soluble organic salts are homo- or co-polymeric acids or their salts, in which the polycarboxylic acid contains at least two carboxyl radicals separated from each other by no more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1 596 756. Examples of such salts include polyacrylates having a MW (molecular weight) of 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.

Detergent fillers in the form of salts are usually included in amounts from 5% to 80% by weight. agent, preferably from 10% to 70% wt. and most preferably from 30% to 60% wt. means.

Saponification suppressor

Another optional additive is a saponification suppressor, examples of which include silicones and silicone/silicon oxide blends. Silicones may generally be alkylated polysiloxane materials, while silica is usually used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials may be incorporated as bulk materials in which the saponification suppressor is preferably releasably incorporated in a non-surfactant water-soluble or water-dispersible detergent impermeable carrier. Alternatively, the saponification suppressor may be dissolved or dispersed in a liquid carrier and applied by spraying to one or more other components.

A preferred silicone saponification control agent is disclosed in Bartolotta et al., U.S. Pat. Patent 3,933,672. Other highly preferred saponification suppressors include the self-emulsifying silicone saponification suppressors described in German Patent Application DTOS 2,646,126, issued April 28, 1977. An example of such compounds is DC-544 commercially available from Dow Corning, which is a siloxane/glycol copolymer. Saponification control systems containing a mixture of silicone oils and 2-alkylalkanols are very preferred saponification control agents. Suitable 2-alkyl-alkanols are 2-butyloctanol, which is available in the commercial network under the trade name Isofol 12 R.

Anti-saponification systems are described in co-pending European Patent Application No. 92870174.7, issued November 10, 1992.

Very advantageous saponification suppressor control agents are described in the pending European Patent Application No. 92201649.8. Said compositions may contain a silicone/silica mixture in a fume-free silica composition such as Aerosil*

The saponification suppressors described above are typically used at levels from 0.001% to 2% by weight. agent, preferably from 0.01% to 1% wt.

Other additives

Other ingredients such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, tarnish reducers, color fixers and/or encapsulated or unencapsulated perfumes may also be used in the cleaning compositions.

Very preferred encapsulation materials are water-soluble capsules containing polysaccharide starting material and polyhydroxy compounds such as those disclosed in GB 1,464,616.

Other suitable water-soluble encapsulation-forming materials include dextrins derived from non-greasy starch of acid esters of substituted dicarboxylic acids, which have been described in U.S. Pat. 3,455,838. These acid ester dextrins are preferably prepared from such starches as soft corn, soft sorghum syrup, radish, sago and potato. Suitable examples of listed materials used for encapsulation are N-Lok manufactured by National Starch. The N-Lok material used for encapsulation contains modified corn starch and glucose. Starch is modified by adding monofunctional substituted groups such as succinic octenyl anhydride.

Anti-soiling agents and soil suspending agents suitable for the purposes of the invention include cellulose derivatives such as methyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose and homo- or copolymeric polycarboxylic acids or their salts. Polymers of this type include polyacrylates and copolymers of maleic anhydride-acrylic acid, previously mentioned as fillers, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, maleic anhydride forming at least 20 mol. % copolymers. These materials are usually used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8% by weight, most preferably from 1% to 6% by weight. means.

Preferred optical brighteners are of an anionic nature, examples of which are 4,4'bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene disodium 2.2'disulfonate, 4,4'-bis-(2morpholino- Disodium 4-anilino-s-triazin-6-ylamino)stilbene-2:2'-disulfonate, 4,4'-bis-(2,4-dianilino-striazin-6-ylamino)stilbene-2:2'-disulfonate disodium, 4',4-bis-(2,4-dianilino-s-triazin-6ylamino)stilbene-2-sulfonate sodium, 4,4'-bis-(2-anilino-4-(N-methyl-N- Disodium 2-hydroxyethylamino)-striazin-6-ylamino)stilbene-2:2'-disulfonate, disodium 4,4'-bis-(4-phenyl-2,1,3-triazol-2-yl)stilbene-2, Disodium 2'-disulfonate, 4,4'-bis-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-striazin-6-ylamino)stilben-2:2'-disulfonate disodium, 2(stilbyl- Sodium 4-naphtho-1',2':4,5)-1,2,3-triazole-2''sulfonate and 4,4'-bis(2-sulfostyryl)biphenyl. Very advantageous optical brighteners are the specific brighteners listed in the pending European Patent Application no.

95201943.8.

Other useful polymeric materials include polyethylene glycols, particularly those with a molecular weight of 100 to 10,000, more particularly 2,000 to 8,000 and most preferably about 4,000. These are used at levels of from 0.20% to 5% by weight, more preferably from 0.25% to 2 .5 wt% These polymers and the previously mentioned homo- or co-polymers of salts of polycarboxylic acids are suitable for improving bleaching, anti-fouling effects and cleaning effects against mud, protein and oxidizable dirt and against the presence of unwanted transition metal impurities. The soil release agents useful in the compositions of the present invention are usually polymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in commonly assigned U.S. Pat. Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A particularly preferred polymer in accordance with EP-A-0 272 033 has the formula:

(CH ₃ (PEG)4 ₃ )o.7 ₅ (POH)o, ₂₅ ((T-PO) ₂ , ₈ (T-PEG)o,4)T(PO-H)o, ₂ 5((PEG )43CH ₃ )o.7 ₅ in which PEG is -(OC ₂ H ₄ )O-, PO is (OC ₃ H ₆ O) and T is (ροΟΟ ₆ Η ₄ ΟΟ).

Also very useful are modified polyesters, such as irregular copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, end groups forming primarily sulfobenzoate and secondarily monoesters of ethylene glycol and/or propanediol. The goal is to obtain a polymer terminated at both ends with sulfobenzoate groups, "primarily" in the present context, most of the copolymers mentioned at this point will be terminated with sulfobenzoate groups. Some copolymers will be less than fully closed and therefore their end group may include a monoester of ethylene glycol and/or propane-1,2-diol, formed "secondarily" of such substances.

Selected polyesters for the purposes of the invention contain approximately 46% by weight. of dimethyl terephthalic acid, approximately 16 wt.% of propane-1,2-diol, approximately 10 wt.% of ethylene glycol, approximately 13 wt.% of dimethyl sulfobenzoic acid and approximately 15 wt.% sulfoisophthalic acid and have a molecular weight of approximately 3,000. Polyesters and the method of their preparation are described in more detail in EPA 311 342.

According to the current state of the art, it is very well known that free chlorine in tap water quickly deactivates enzymes contained in cleaning agents. Therefore, the use of chlorine carriers (acceptors) such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine at a level of approximately 0.1 wt.%. of the total agent in the formulations will ensure increased stability of the carbohydrase during washing. Compositions containing chlorine carriers are described in European Patent Application 92870018.6, issued January 31, 1992.

Alkoxylated polycarboxylates prepared from polyacrylates useful for the purposes of the invention provide additional anti-greasy effects. Such materials are described in WO 91/08281 and PCT 90/01815, pp. 4 et seq., in the footnoted text. Chemically, such materials contain polyacrylates having one ethoxy side chain for every 7 to 8 acrylate units. The side chains have the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2 to 3 and n is 6 to 12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb structure polymer. The molecular weight can vary, but typically ranges from about 2,000 to about 50,000. These alkylated polycarboxylates can comprise from about 0.05% to about 10% by weight. of the stated funds.

Emollients (fabric softeners)

Fabric softeners may also be incorporated into laundry detergents in accordance with the present invention. These agents can be of the inorganic or organic type. Inorganic softening agents are exemplified by the smectite clays disclosed in GB-A-1 400 898 and in US Patent 5 019 292. Organic fabric softeners include the water-insoluble tertiary amines disclosed in GB-A 1 514 276 and EP-BO 011 340 and their combinations with mono C ₁₂ -Ci ₄ quaternary ammonium salts are disclosed in EP-B-0 026 527 and EPB-0 026 528 and long chain diamides disclosed, e.g., in EP-B 0 242 919. Other useful organic admixtures of fabric softening systems include higher molecular weight polyethylene oxide materials, e.g. disclosed in EP-A 0 299 575 and 0 313 146.

Clay smectite levels are typically in the range of 2% to 20% by weight, more preferably 5% to 15% by weight, the material being supplied as a dry admixture to the rest of the formulation. Organic fabric softeners, e.g., water-insoluble tertiary amines or di-long chain amide materials, are incorporated at levels of from 0.5% to 5% by weight, typically from 1% to 3% by weight, while polyethylene oxide materials with high molecular weight and water-soluble cationic materials are supplied at levels from 0.1% to 2% wt. usually from 0.15% to 1.5% wt. These materials are usually supplied to the spray-dried portion of the composition, although in some cases it may be more advantageous to supply them as a dry mixed bulk material or to spray them as liquid liquids to the other solid components of the composition.

Washing method

The compositions of the invention can be used in essentially any washing or cleaning process, including soaking methods, prewash methods and methods with rinsing steps, for which a separate rinsing aid can be supplied.

The process described in the text includes soaking the fabrics in the washing solution in the usual way and verified examples under these conditions.

The method of using the composition according to the invention is conveniently carried out during the cleaning process. The cleaning method is preferably carried out at a temperature of 5°C to 95°C, especially between 10°C and 60°C. The value of the pH factor of the solution intended for use is preferably from 7 to 11.

A preferred dishwashing method involves treating the soiled article with an aqueous liquid in which an effective amount of an automatic dishwashing agent or rinse agent is dissolved or contained. Usual effective amount

------a product intended for -dishwasher-disinfection—3-to- 60 g of the product—dissolved—or —dispersed in a washing volume of 3 to 10 liters.

According to the method of manual dishwashing, the effective amount of dishwashing detergent applied to dirty dishes, usually from 0.5 to 20 g (per 25 pieces of treated dishes). The preferred method of hand dishwashing involves applying a concentrated solution to the surface of dishes or soaking in a large volume of a diluted detergent solution.

The following examples verify and exemplify the present invention, but the invention is in no way limited by the given examples, nor is its scope limited by them.

Enzyme levels in detergents are expressed by weight of pure enzyme of total formulation and, unless otherwise specified, detergent additives are expressed by weight of total formulation. The folder abbreviations used in the resources have the following meanings:

FOREST

TAS

CXYAS

25EY

CXYEZ

XYEZS

QAS

Soap

A non-ionic substance

CFAA

TFAA

TPKFA

DEQA

SDASA linear Ci ₂ sodium alkylbenzene sulfonate sodium tallow alkyl sulfate

C _1X -C _1Y sodium alkyl sulfate

C12-C15 predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide C _1x -Ciy predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide

C _1X -C _1Y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole of R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) with R ₂ =C ₁₂ -C ₁₄ linear sodium alkyl carboxylate derived from 80/20 mixture of tallow and coconut oil.

C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the trade name Plurafac LF404 by BASF Gmbh.

C ₁₂ -C ₁₄ alkyl-N-methylglucamide

C ₁₆ -C ₁₈ alkyl-N-methylglucamide

C ₁₂ -C ₁₄ reduced fatty acids di-(alkyl tallow-oxyethyl)dimethylammonium chloride

1:2 ratio of stearydimethylamine:triple pressed stearic acid

He didn't hold back 45-13

Silicate NaSKS-6 Carbonate Hydrocarbonate

STPP

MA/AA

PA30

Terpolymer

480N

Polyacrylate

Zeolite A

Citrate

Citric acid PB1

PB4

Percarbonate

TAED

NOBS

Photoactive bleach

PAAC: Ci ₄ -C ₁₅ linear primary alcohol ethoxylated, sold by Shell Chemical Co.

: amorphous sodium silicate (SiO ₂ :Na ₂ O ratio = 2.0) : crystalline layered silicate of the formula 8-Na ₂ Si ₂ O5~ ------- : anhydrous sodium carbonate with a particle size between 200 pm and 900 pm: anhydrous sodium bicarbonate with a particle size between 400 pm and

1200 pm : anhydrous sodium tripolyphosphate : 1:4 maleic/acrylic acid copolymer, average molecular weight about 80,000 : polyacrylic acid with an average molecular weight of about 8,000 : terpolymer with an average molecular weight of about 7,000 containing acrylic:maleic:ethylacrylic acid monomer units in a weight ratio of 60:20:20.

: a 3:7 irregular copolymer of acrylic/methacrylic acid, average molecular weight approximately 3,500 : a polyacrylate homopolymer with an average molecular weight of 8,000 sold under the trade name PA30 by BASF GmbH : hydrated sodium aluminosilicate of the formula

Na ₁₂ (AIO ₂ SiO ₂ ) ₁₂ .27H ₂ O having a primary particle size ranging from 0.1 to 10 micrometers : trisodium citrate dihydrate with a strength of 86.4% with a grain size between 425 pm and 850 pm : anhydrous citric acid : anhydrous bleach sodium perborate monohydrate, empirical formula NaBO ₂ .H ₂ O ₂ : anhydrous sodium perborate tetrahydrate : anhydrous sodium percarbonate bleach empirical formula 2Na ₂ CO ₃ .3H ₂ O ₂ : tetraacetylethylenediamine : nonanoyloxybenzenesulfonate in the form of sodium salt : sulfonated zinc phthalocyanine encapsulated in a soluble polymer dextrin: cobalt pentaamine acetate salt

Paraffin

BzP

Pectinesierase

Protease

Amylase

Lipase

Cellulase

HEDP

DETPMP

PVNO

PVPVI

Brightener 1 Brightener 2

Silicone anti-foam agent

Granular saponification suppressor

SRP 1 : paraffin oil sold under the trade name

Winog 70 by Wintershall : benzoyl peroxide : pectinesterase-α~PG764, P1889 or P5400 from orange peel available from Sigma; P6763 from tomato available from Sigma or the pectinesterase described in DE 30 44 455.

: proteolytic enzyme sold under the trade names Savinase, Alcalase, Durazym by Novo Nordisk A/S, Maxacal, Maxapem sold by Gist-Brocades and proteases described in patents WO 91/06637 and/or WO 95/10591 and/or EP 251 446 : The amylolytic enzyme sold under the trade name Purafact Ox Am ^R described in WO 94/18314 sold by Genencor; Termamyl®, Fungamyl® and Duramyl®, all products available from Novo Nordisk A/S and others described in WO 95/26397 : Lipolytic enzyme sold under the trade name Lipolase, Lipolase Ultra by Novo Nordisk A/S : Sodium carboxymethyl cellulase; 1,1-hydroxyethanediphosphoric acid; Diethylenetriaminepenta(methylenephosphoric acid) sold by Monsanto under the trade name Dequest 2060 : Poly(4-vinylpyridine)-N-oxide : Poly(4-vinylpyridine)-N-oxide/vinylimidazole and vinylpyrrolidone copolymer : 4,4'-bis(2- sulfostyryl)biphenyl disodium : Disodium 4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)stilbene-2,2'-disulfonate : Polydimethylsiloxane foam control agent with siloxane- with an oxyalkene copolymer as a dispersing agent and a ratio of said antifoam control agent to said dispersing agent from 10.Ί to 100.Ί : 12% silicone/silicon oxide, 18% stearyl alcohol, % starch in granular form : Esters terminated with sulfobenzoyl end parts

SRP 2

Sulfate

HMWPEO

PEG

BTA

Bismuth nitrate NaDCC

Enveloped perfumed particles

KOH pH with oxyethyleneoxy and terephthaloyl backbone : Diethoxypoly(1,2-propylene terephthalate) short block polymer : Sulphate anhydrous — — : High molecular weight polyethylene oxide : Polyethylene glycol : Benzotriazole : Bismuth nitrate salt : Sodium dichloroisocyanurate (cyanurate - cyanuric acid salt) : Insoluble fragrance delivery technology using zeolite 13x, perfume and binder filler dextrose/glycerin : 100% active potassium hydroxide solution : measured as a 1% solution in distilled water at 20°C

Examples of implementation of the invention

Example 1

The following liquid detergents have been made in accordance with the invention:

í Folder . ?, >- / // ’ in .......j VI i LAS I - i 8.0 ^Xór ' 8.0 8.0. ¹ 8/) 8.0' - , C25E3 _{t r} 3.4 3.4 · < . 3.4 3,4, 3.4 3.4 > QAS -- v — 0.8 \ 0.8 HlIBSli 0.8 0.8 Zeolite A, 18.1 18.1 18.1 16.1 18.1 18.1 i Carbonate 13.0 13.0/.: 13.0 - -27.0 27.0 27.0 «Silica - 1.4 1.4' 1.4 3.0 3.0 3.0 í Sulphate ' / ' ,~, A 26.1 26.1; r · 26.1 26.1 26.1 26.1; i ' *> 7 2s~ * -w ; PB4/.J. 9.0 9.0 9.0 9.0 9.0 '9.0 , TAED í J - » DETPMP. 1.5 1.5 1.5 White 1.5 1.5 0.25 0.25. 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 ^of 0.3 0.3 0.3 0.3 Pectinesterase., «; 0.005 0.01 0.05 0.01 0.02 0.08 ’ Protease 0.0026 0.0026 0.0026 ' 0.0026 0.0026 0.0026; Lipase 0.003 0.003 0.003 „ 0.003 0.003 0.003 Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009' , MA/AA 0.3 0.3. 0.3 0.3 0.3 0.3 ; CMC 0.2 0.2 0.2 0.2 0.2 . 0.2 : Photoact.béiídloíppm) 15.0 15.0'' 15.0 15.0; 15.0 15.0 ¹ ί ij,-; Her, '. J ' Brightener 1 0.09 0.09 0.09 0.09. 0.09 0.09 • Perfume 0.3 0.3 0.3 .......0.3 - 0.3 0.3 Silicone agent 0.5 0.5. - 0.5 0.5 0.5 0.5 » against foaming. ΑΑ , '-'ύ-'-Ή ⁴ '''7'''''r“1'.! P i ^{1 J} fj ; Mixed Minority Under· up to 100% up to 100% up to 100% up to 100% up to 100% dó^'oo.%? j Density in g/l ' * 850 850 850 occ 850 850 Ο?0;Λ :

s. j ί, n ”

Example 2

The following granulated laundry detergents with a volume density of 750 g/l have been prepared in conjunction with the invention:

...../........

5.25

1.25

3.25

0.8

19.7

6.1

6.8

39.8

5.0

0.5

0.25

0.001

0.0026

0.003

0.0006

0.0009

0.8

0.2 ppm

0.08

iii 5.61 4.76 1.86 1.57 2.24 3.89 0.76 1.18 5.0 — 2.0 19.5 19.5 10.6 10.6 21.4 21.4 2.0 2.0 íSlilIBSS# — slSOBSBšIší 14.3 12.7 — 3.1 — 0.2 0.2 0.3 0.3 0.02 0.005 0.0085 0.045 0.003 0.003 0.0006 0.0006 0.0009 0.0009 ΙβΙΙΒΙ 1.6 0.4 27 ppm 27 ppm 0.19 0.19 0.04 0.04

Wrapped perfume particles _j - 43 0.3 0.3 SHIkpnoVý-przedekbyř ¹ 0.5 2.4 antifoam = Mixed minority interests up to 100% up to 100% to-100% -

»

Example 3

In accordance with the present invention, the following cleaning formulations were prepared, in which formulation I is a phosphorus-containing cleaning agent, formulation II is a zeolite-containing cleaning agent, and formulation III is a concentrated cleaning agent:

Perfume

Dry ingredients

Carbonate

PB4

PB1

TAED

Photoactive bleach

Pectinesterase j

Protease Lipase ,JI , \ Č '{'i ¹ 1 J m/J í pí , _rl j „ i li I '3 p X ,

Amylase..

Dry mixture of soúnébb sulfate

/ ......~'1BIíIBMí|^K........ ··- 24.0 24.0 - — 24.0 — 9.0 lIIIBUBl! 13.0 2.0 lliSHIBill 2.0 6.0 11.0 2.0 iiiiiiiiiiiiiii — 7.0 l|IÍ||iil|lttB 3.0 1.0 lillilll Drooling 0.5 0.2 I11ISSIII· 0.2 1.0 lllSIMIlli 1.0 0.4 ΙΙβββΙΙ 0.2 2.5 !88|IM|Clay 2.0 2.5 1II1ISBSII 2.0 0.3 ΙβΙΙΒΙΙΙ! 0.3 0.3 ^; ili!llS8li!B 0.3 6.0 13.0 15.0 18.0 18.0 10.0 4.0 Ιι·ΙΙΙ·!·Ι — 3.0 3.0 1.0 0.02 0.02 0.02 0.05 0.05 0.01 0.01 0.01 0.01 0.009 0.009 - 0.009 0.002 0.003 0.001 3.0 IIIIBIIISi 5.0 up to 100% up to 100% up to 100% 630 630 630

Example 4

- In accordance with the previous invention, the following cleaning formulations were prepared not containing; S/OŽRý, ;

i- ; ^r í

- ·» ——*

ΙϋβΙΒ· ninini

ZeoliteA

f. 7 A

.........Ϊ......

15.0 ' in Ή ^r ' V ^ø 4 '*i ! 5 * / ' A ⁴ .,-,/ 4'*p »1 , .

- _r - ε , . 15.0

-.»t......

(Sodium sulfate, j .-.Jř» ¹ '*'

DETPMP

J- ; CMC

81¾¾¾¾ bìMA/AA ( .

I-War;

C45AS

-* I ,

-y. <

íí^1?4í;S?&:íS.« X·:

: FOREST.

TAS

Silicate ^; ZeoliteA

CMC

MA/AA

Carbonate

Sprayed .3* i Perfume , C45E7

C25E3

Dry ingredients

MA/AA t !' “ J»' J ¹ /''

0.0 3.0 0.4 0.4 5.0 - 'í , I ¹ 4- jS-L * v 4 .0.5 λ'.7>íΆ' 4.0 ϋββΒϊϊΙ B· — 11.0 6.0 * ' i*»*· ^41, *í.sf “ » ·, i 1 — 3.0 2.0 — 4.0 ',Η 4 .¼ ' - >' -, f-Ί„kS··* A ⁴ »1j l *, , -n - fig. * ^T and "i * — 10.0 ; 15.0; - 13.0 — |||1111||Ι|3ΙΙΙΒ8ί 0.5 — SliiiftóeMBSwSSffif 2.0 9.0 7.0 l ^J V , i J * > -/. e ^J 4ýj _t ; her . 7.0 0.3 '0.3' 0.5 4.0 4.0'' 4.0 2.0 2.0 2.0 ___ < 2 '7 Λ 3.0 *? ίηί.-'ί· ίνΊι<”|.· A&H&f4 ^r _ , 4·' - /- ¹ 'T ' CJiw7 12.0 10.0 8.0 7.0 ' Y, Tr > ^3.0 < - 5.0 8.0 7.0 0.5 -Z... A5-.':.-ř/ '. . -v :-·.-.χ'-.-,ί,<... .’ . 0.5 0.05 ^: ^.<;0;οό5^;·-· 0.02

46 Protease) .,. - 0.026 0.016 0.047 Lipase.. 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase. . - * 0.006 0.006 0.006" Silicone agent WSwWí^i^ií^^ $ ^: $ ^; ^ί;$ί!·$$'&ψ$ ÍORŘ^ii^l^W^' 5.0 SliiBliBjBM 5.0 against foaming < Dry ingredients Sodium sulfate — HISMi — Balance (moisture/mixed) up to 100% up to 100% up to 100% Density (g/l) 700 700 700

Example 5

In accordance with the present invention, the following cleaning formulations were prepared:

Folders / // ..............lil................... /IN 20.0 14.0 24.0 22.0 QAS 0.7 Ί, Ο — lijlfc TFAA — 1.0; , — ffiSiiftUII C25E5/C45E7 — -2.9^ — ιίβι C45E3S — ~ and \ — STPP Silicate 30.0 9.0 - 5.0 30.0 10.0 22.0 jjjMi Carbonate 13.0 7.5/.,. . — iil^e Hydrocarbonate. < — ιι^Λϋ — DETPN1P 0.7 1.0 — August 4 ¹ - - 0.3 18¾¾¾¾ — MAIA? \ 2.0 2.0 CMC 0.8 '0.4; ~' 0.4 0.2. Pectinesterase 0.08 0.04'. 0.05 0.01 Protease 0.008 0.01 0.026 0.026 Amylase 0.007 0.004 — 0.002 Lipase 0.004 0.002 0.004 0.002 Cellulase _t . 0.0015 0.0005' — Photoactive bleach (ppm)' 70 ppm 45 ppm — 10 ppm Brightener 1 0.2 0.2' 0.08 0.2 PB1 6.0 2.0 — ^ΙΙββδβ NOBS 2.0 1.0, — ΐΐϋΐΚΒίβί Balance (moisture/mixed) up to 100% up to 100.% up to 100% up to 100% 1 JiÍffUifctfjĚflťfcyjlŮÍlifeďiSéiHii:

Example 6

In accordance with the present invention, the following cleaning formulations were prepared:

Folders II r..... _Ul IV Blown bulk material íBSSIíJSBBBBm Zeolite A 30.0 22.0 · . 6.0 They grew stronger NaSKS-6 — — iisimsii Polycarboxylate — . — Λ rí — iUlBISB Sodium sulfate 19.0 .5.0 7.0 ΙΒβΙίΜΙΙβίΙΙΜΙβΒ MA/AA 3.0 3.0 3.0 siSIRiiSHlISS lilies 14.0 12.0 22.0 21.5 C45AS 8.0 7.0 7.0 11¾¾¾ A cationic substance — — forest Silicate — 111111¾¾ 5.0 — . —C ~ : 2.0 11¾¾¾¾¾¾¾¾¾ ' Clarified· ¹ > * / , - ¹ , 1 Μ -ρ ί ⁺ i ? ! 1 ^J , ¹ 0.2 0.2 0.2 ΟίΒΙϋΙΪΒΙΒΐ Carbonate 8.0 16.0/. 20.0 ; 10.0 DETPMP — 0.4 0.4 Sprayed C45E7 1.0 . it 1.0 3.2 Dry ingredients PVPVI/PVNO 0.5 0.5. 0.5 ' 7 i 'Pectinesterase' ¹ 0.005 0.01. - 0.01 0.005 Protease 0.052 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 0.009' Amylase 0.001 0.001 0.001 0.001 i , Cellulase 0.0002 0.0002 0.0002 0.0002 ? l NOBS — 6.1' - 4.5 - 3.2 '/'J PB1 ¹ - 1.0 ' 5.0 ^; ; 6.0 3.9 · j ί Sodium sulfate 'O% p. — 6.0. .. — into balance. ’ Balance (moisture/$mixed), up to 100% up to 10G/>Ž - up to 100% •:u^^í^í#^»»^^w»!4:iííWííí SA»»»

Example 7

In accordance with the present invention, the following concentrated cleaning formulations containing bleach were prepared:

Folders / iiiiiiiseiii III Blown bulk material Zeolite A 15.0 15.0 15.0 Sodium sulfate — SHUfcilli — SlilllSlSSBlB 3.0 3.0 — MlIŽljlill 1.5 DETPMP 0.4 aMj|l|ÍŽlli|j 0.4 0.4 ensl^eiii 0.4 MA/AA 4.0 lliiiMSg 2.0 Deposits 5.0 jillMiSil 5.0 'SeeieJlIlHiillili 2.0 ilIliBill 1.0 Silicate 3.0 lllIJSiSlllíj 4.0 Zeolite A 8.0 !II11IÍÍIS!I 8.0 Carbonate 8.0 8.0 - 4.0 Sprayed Perfume 0.3 0.3 0.3 C4SE7 2.0 2.0 i 2.0 C25E3 ~ *' _: ^r '~ ¹ 7¾ ' χ 2.0 ¹ st a — Dry ingredients Citrate 5.0 13ϊΐΙ/!^ΙΙβ!!!1ΙίΙ· 2.0 Hydrocarbonate — 3,Q — Carbonate 8.0 15, about; at '* ⁴ 10.0 TAED 6.0 2:0 ^; ' 5.0 PB1', 14.0 7.0, , 10.0 Polyethylene oxide, ’/ — 0.2 (MWSOOOOOOmoIhmoÉh.) , * Γ ^r Ti\ ^J Bentohttpy clay i.;-;·;·,' ««. Bfefe^ssfiíistea#i se Xý kXy yI-u— , l·“' ,3 r ^ø 10.0 Pectinesterase 0.005 0.08

50 Protease, 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.0.02— . -0.002 - ----A002 Silicone agent 5.0 5.0 against foaming Dry ingredients Sodium sulfate — ΙΙβ!8Ι! — Balance (moisture/mixed) up to 100% up to 100% up to 100% Density (g/1) 850 850 850

Example 8

Folders............ " 7" / ........................'||ljlllBlpttOBBiil Deposits C45AS 11.0 Zeolite A 15.0 !ΙΙΙϋ^Β1β·Ι Carbonate 4.0 ililsIBlISilliSS MA/AA 4.0 1M|ftlil8l8BBŽiiiftfc|MlBSIIi|lj 0.5 9|Sl!Éljl8ljll81l DETPMP 0.4 ΙΙΙΙΙΙβΙΟίΙΐ! Sprayed C25E5 5.0 Perfume.. 0.5 811¾ Dry ingredients HEDP 0.5 Wjjl|ÉM8S||||j^M|ijj|BB SKS-6 13.0 lliaiiBlBIsiiSi Citrate ' ^f '· 7\A - \ , — v ¹ ~, ^r , 1 í 3.0 TAED 5.0 118¾^ Percarbonate - ' , 20.0 20.0 SRP1 0.3 J|jg^ Pectinesterase « ?- - 0.02 llllBilIlilliilillI Protease ¹ ·.·'·<-<.·· '//- ' 0.014 ΙΙΙΙΙΙΙΙΙβΙΙβΙίΙΙΙΙΙΙ^ « '^7' i*^Knows \ jj*' i - ⁱ «>·-' Lipase ~ 0.009 0.009 Cellulase 0.004 0.004 Amylase - ’ '-1' ΐ y·' 0.005 0.005 Silicone agent 5.0 0.2 0.2 up to 100% 850 ISil!ltSS|fel8$ŽlBl ΛΙβιίΒίίΙΙβίΛΛκβίΜίΒΙΒ^ΚβΜ^ΑΛΜ! . .' .0.2 -.'.' , -· . cio.100%;·:··. /.. · . ,-,.... J- ...... v, . . ^: ;.'. 850 i¥íiesWS»swKWwosíSwSBeSSBft«

Example 9

--Consistent. With the present invention, the existing formulations were used:

* S/ožfcy ' ~~.....and.............“ // lil ............'] IV .....in..........'........ 21.0 25.0 , ' 18.0 18.0 — C ₁₂ -C ₁₄ alkyl sulfate coconut, oils with 1 4 JÍ ^{1 J} 1 * ¹ J „ '•«J?4 — lllBBIIi — IISIUBI 21.9 ί ΑΕ0/“ ' , . V ¹ //i/ίΐίΊ-ί^ί^ίΙ-'ΐίίΠ^'Μ^^Ι^ί^ΐΙΐ^ί!^ — /1:¾¾¾¾¾¾ 1.5 1.5 2.3 . Decyldimethylhydroxyethyl ¹ ι' I 4/» j 1 1 11 _{( lt} ** ' 4 — 0.4 0.7 0.7 θ, θ ; NH ₄ +CI Ϊ fc l UJL ^1Í J -* . A non-ionic substance 1.2 0.9 0.5 ' C ₁₂ -C ₁₄ fatty alcohol — - — - ’ '· — 1-0 , coconut oil [sT^yy '''yyy-- 44.0 25.0·. . 22.5 22.5 22.5 Zeolite 7.0 10.0. — -lip-' 8.0 ' MA/AA , . ' ' — 0.9 0.9. — SRP 1, 0.3 0.15 0.2 0.1 0.2 CMC 0.3 2.0 0.75 0.4 1.0 Carbonate 17.5 29.3 5.0 13.0 15.0 Silicate 2.0 — 7.6 7.9 — Pectinesterase 0.005 0.01 0.007 0.01 0.01 Protease 0.007 0.007 0.007 0.007 0.007 _t Amylase — 0.004 0.004 0.004 0.004 1 Lipase 0.003 0.003 0.003 - —'.' — Cellulase — 0.001 0.001 0.001 0.001 NOBS — /x&F/i/isf — 1.2 1.0 PBI — xfffSgsf/ — 2.4 1.2 j Diethylenetriamine acid, — — 0.7; 1.0 i pentaacetic 4 / *· ^J á ' -íli * t - Diethylenetriamine acid- :' 0.6 : pentamethyl phosphorite Τ-?2^/Δ/>3ΐδψ^|1ψ5Λ^«^ίί; ^: 1·4·ίιΐ^ΐί^^ζ·;'(ί^^·ζ ^: ΐίί^^3ί)4ί'Μ^ι)ί^?ίΓί5ΐί3ί'ΐ;^ί·ίΜ8Ψί ^: · WBtWBSWWtíSW — 0.8 • ‘ '-Τ’Τ, no’ — ’ Photoactive bleach(s). 45 50 15 alMBlIBI 42 Ι;:.;,. :·. ί':ί.^'Λ5{ί;'4<:?^ΙτρίΑζίΚίζ:Γ;1ίλ1 ₁ !·Η:ί·ΐ;':'!'3ΐ.^'ί^/!3,:5,'Β:·,' ^ί í|. 0.05 ” r-' ’ - 0.04 0.04 0.04

0.1

0 ₄ 3 .

0.05

0.13 ,

Water and minority 'impurities* dol00% to 100% ' to 100% to 100%'

0.13 to 100%

Example 10. In_soiiiádu with the presented invention, pňp.ca.vfinyj>ásleduiífi^ - -.....

: Components ø -t ⁱⁿ » ¹ ø , ?„ / n III IV IN w VII He poured l 4^'^ Ί l· 10.0 13.0 9.0 25.0 ®M®|se — HiSII Č25AS T ŚČ·'·:'!'•••Η.·;/!'/’?;/· 4.0 1.0 2.0 10.0 — 13.0 18.0 15.0 ||^^j^|J||||l||Il;]5|| 1.0 j-,- — 3.0 — 2.0 2.0 4.0 6.0 8.0' 13.0 2.5 — — 4.0 4.0 ] ⁽ — • — 4.5 — 6.0 8.0 8.0 ! qXs^// ^j 'Ι'.νίί'-ί-ί'/ί^^i'';Č17 ^? ''-3'':í<^; .:L ύ·.-;::·<'· ₍ < — filiiSII — ~ - 3.0 . it — iiiisis TPKFA ^: f eats, «„( , tjji 2.0 ’.íí:'Wo>m > , .· , 13.0 2.0" — Ί 5.0 7.0 7.0 Fatty acids | ¹ i ¹ 'φ r* *1 >Ί; rapeseed oil . y. — 5.0 — — 4.0 4.0 j Pitonic acid 2.0 3 o 1.0 1.5 1.0 1.0 1.0 1.0 ' Dodecenyl/tetra, decenyl amber acid 12.0 10.0 15.0 Oleic acid 4.0 2.0 1.0 — 1.0 ΒΒΙ — eimia Ethanol 4.0 4.0 7.0 2.0' 7.0 2.0 3.0 2.0 1,2-propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0 Monoethanolamine — — — 5.0 — — 9.0 θ, Ο Triethanolamine' — balder 8.0 SSB8Í1I — — — forestBis NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2'? ¹ * Polyethoxytetra- .j.··. .'::: ,:: : i; ^;í K' _: :'*·<:/'ty/'·''·...' ethyienpentaamine 0.5 0.5 0.2 — —— 0.4 DETPMP 1.0 _; 1.0 0.5 1.0 2.0 1.2 1.0 ¹ SRP 2 0.3 — 0.3 0.1 — — 0.2 2 PVNO and :':i;.':'.y;··.!;*i,!*'('/·'Čij··''·'ϊ'^'ί'ΐ';·:j·? *'3; — — — — — ΙΙβΐΜΒ — and Pectinesterase 0.005 0.005 0.005 0.005 0.05 0.07- 0.02 , Protease , 0.005 0.005 0.004 .0.003 0.008 0.005 0.003 0.006 — 0.002 — ' 0.0.01 — W-W f. 0.003 0.003 0.002 0.002 0.005 0.004 0.002 ο, οοβ; 0.005 , 0.005 ΒΙβΙβΙ — \ 1 ^year —. 0.0001 ... 0.0001 0.0001

í V '•'' Lh-L ø” . and

Balance ' ύ Λ ·* j

0.1

SuMndaenijlfSĎS ,0.2

0.015 i to t:(v|hWsW^MW;W ι°ο ^% to to 100% 100%

1.0

<2.0' 1.0 1.5,. 2.5 2.5 Mr ___ ___ oh — , ij, j Z. — A.o.. -,4,0.- - (ββίί 0.6 0.3 — ijMlíiiWžS; to to to to to 100% 100% 1Q0% 100% 100%

Example 11

In accordance with the present invention, granular cleaning agents for fabrics providing the ability to soften them during washing were prepared:_____-__:_ _____.....- . _ ........

¹ 7' 1« J _fl Ij _d ^„,1 *-j4,(.' _w Fíi -i

ί Coconut oil alkyl- / ; dlm^dtyihydroxyethylammony

7.6

1.3 4.0

1.4

J 'LďífíW ,7„ r,'

EtO®S’ iWi ϊί

BBSI5WS

.....í u.í .:

MA/AA

DETPMP

PB1

LL; <;ί j: ^: ·:

, Percarbonate , TAED

Smectite clay ’ HMWPEO , ; Pectinesterase y-y.y ypgi'·ν.ψi;':-:.:A,;;!!.zL·;?.;/1. ·':

Protease

Lipase

Amylase - Cellulase í Silica \ Carbonate

( r $ 1 Jr' ^1, * * , <,<4'

5.0

15.0

4.0

0.4

15.0

5.0

10.0

0.01

0.02

0.02

0.03

0.001

3.0

10.0

1.0

0.2 to 100% //

10.0

5;0

1.0 hp

3.0

11.0

15.0

4.0

0.4?

15.0

5.0

10.0

0.1

0.01

0.1

0.2

0.005

5.0

10.0

4.0 jjBjM to 100%

White

Example 12 , — In accordance with the set-3/.yaá!ezero^JiyL4\6.pra.'/en nextlex^icL^ost of fabric softener supplied during rinsing:

[\Folders > ’ < CQ - íLl*, “'i , 'Active emollients 20.0 5 Pectinesterase 0.01 | Amylase. <; < ?·;//v. . . 0.001 pCellulase XjďQCC',.. ¹ , ^: 0.001 IBÉI1!!I!!ÍIS 0.03 j Anti-foaming agent ' ; -- 0.01 í Blue dye. . ~ \ : τ tt , ·” Λ' Τ. ·, ¹ . 25 ppm ÍČáČí ₂ , ' . 3¾i·,' : i _ , „ „ 'VkR i Perfume -v-, 0.20 0.90 5 Vqda/mlnorite shares up to 100%

Example 13

- In accordance with the above-invention, the following fabrics have been produced: -

1,7//' Deqa ' Wí ^lř *' “ 'ΗΛίγνύ-/·.^' 2.6 ........'’’1ΙιΙ81|ι|Ι!Ι| 19.0 III 70.0 ÍSefe· ⁴ '^ ¹ ; ": ·' 0.3 1¾¾¾¾¾¾¾¾¾¾¾¾ — 0.02 0.02 13.0 /. /Λ ——— *··\ 1.0 LwfeisiÍ · · Perfume ' - .'"·-' P Lwwiii ” ' ''' — lllIBBilB — 0.005 0.05 0.01 1.0 1Ϊ1ΒΙΙΒ 0.75 ϊ . jentafait “— >β|1(Ιβ|β5ΒβϊΙ8ΒβΙ 0.38 Silicone agent against .....- '-··-«;-·-·· - <·-- 3,· -vivináWXWH*” · ip ^r >> i . - .iM. 0.01 0.01 · . Electrolyte ΡΪ^ΐ^η1ί!5Ϊ^ίί^?ί;''ί- ^Ι 5? ^, 7-ι; ^: ί1' ί Ί-Ιί-Ρ· — 600 ppm — í Dye 100 ppm 50 ppm 0.01 Water aminorite shares up to 100% up to 100% up to 100%

Example 14

In accordance-with--the!forementioned---by!ezerR-fey(y--are ^! made-to".

i S/ožÁy·' ~ ^. ....../.............'........ // - , ·· · 1,ιό./>1^4βΐϊϊίι^ν-'^ΐ''20.0; ¹ lil IV ; C26AS '' „ ' Í ' ! í <- * ’ 20.0 20.0 20.0 ! CFAA / ' ^: *' / J. , "" -4. . ~ — ¹ J ! Her 5.0 . j»-; ·' j r i rf 5.0, - 5.0 5.0 i LAS (C11-13) - ζ ¹ ' \ lf* 10.0 10.0 and . -SaSSjBMsieíBilt 10.0 10,C ; Sodium carbonate 25.0 250 25.0 25.0 • Sodium pyrophosphate, 7.0 Th-5** · ··? iiSIlSiliBil lillilSI "βϊΗί^Βίβίί,βίββΐ· 7.0 iIIMI fSTPP<'' - i .<'r-'' „ . - ·\.« _Λ 7.0 7.0 IljljMj , Zeolite A 5.0 n. -?ι ^υ 5.0 5.0 ť ¹ ' ? . 1 * ¹ Ή 1 ? ¹ 0.2 0.2 0.2 0.2 ' Poiyakiylate(MW14pO, ί molecular weight)' b- _v 0.2 0.2. ilíiSSltell 0.2 0.2 Coconut monoethanolamide 5.0 :ί?ΰ«88ββ&ίΙβ’|Βΐ .5.0-,/ 5.0 5.0' • oils 7' ¹ .•'-.Abí'-' * Ί, -?’'.γΊ^ι ' «'Λ??/ Pectinesterase 0.1 o,1 , - 0.15 zoU* / Amylase 0.01 0.02- 0.01 0.01 Protease 0.3 '', 0.5 0.05 ; Brightener, perfume 0.2 0.2 0.2 ,0.2 / 5 CaSO ₄ 1.0 '' Λ» „í K*· * ' ⁽ í|, 0' M-* ⁷ .f 'r 1.0 . 1.0 , J MgSO ₄ ' - · ·; '-<' 1.0 1.0 • , * < 1.0 - Water 4.0 , 4.0' ,/ 4.0 4.0/ filler* up to 100% up to 100% up to 100% up to 100%

The filler can be selected from the group of usual materials, e.g. CaCO ₃ , talc, clay (Kaolinite Smectite), silicates and the like.

Example 15

In accordance with the presented Ra--examination, the following (0.96~kg/l) dishwashing detergents I to VI would, for example, be allowed:

Folds the liÉigiUs

STPP, T

ΓΓϊγ ί” - -, sáaaíseBOiSiiéí isagiiMiiaas i ^3h yjr B ^{1 %}

Citrate , ' , ^z μ 1;λ·ki,,™ , \

Carbon f ^)ři ' ¹

Silicate , , ,

^j Peroxide «-Tj, 'ι Neionto^lAtka liBMlSl! lili +Φ,4ι' „i .,1, ⁴ ,ι!.6

DETPMP PAAC BzP ¹

J 1 ». . , lily

-dj'K

Paraffin }'FiF”H2F’'í^|H§ísý:/ÚÚ

Pectinesterase I Pipteáwr.

jKsfilSSilfcRaí

,. .......... ;;j.t: .μΑ'ΐι:';';

Lipase Amy BTA

Amylase

7/' ' πΓ...... IV ..... V VI — IS^sSelBí 49.0 38.0 — 33.0 17.5 — ilSIliBt 54.0 25.4; — 17.5 — 20.0 14.0 25.4; 33.0 14.8 20.4 14.8 14.8 BBj-rÝ -ί·; Ί — 2.5 2.5 ms· — 1.9 97 7,8 14.3 7,8 . ' í 8.6 — lil·!®! — — — — 6,7 1.5 2.0 1.5 1.5 Λ6Β j 4.8 2.4 - 2.4 ϋΐΒΙΙΙ 2.4 4.0' : 0.8 1.0 0.5 ΐΙ||1|ϊ|||ί — ·//’-' í, *· 1 0.6 0.6 — 11¾¾¾¾¾ — — — θ.2 — — iBíéÓiB — 4.4 — /SOB® 0.5 0.5 0.5 0.5 0.5 0.2 0.07 0.05 0.1 0.1 0.08 0.01 · 0.075 0.05 0.1 0.1 0.08 0.01 _s — 0.001 — --0.005 — • ' —·’ϊ 0.01 0.005 0.015 0.015 0.01 0.0025· 0.3 0.3 0.3 0.3 0.3 — — 0.3 — — — иббиби 4.0 — - — , — ΙβΜΙΙΒβ — 1¾¾¾¾¾ — 4.0 — -· ’\;í — 6.0 2.8 1¾¾¾¾¾) — ¹ «nw«« · * I 7.1 20.8 8.4 * 0.5 1.0; swíoshiSrf 10.8 11.0. 10.9 10.8 10.9. 9.6

Example 16 _\Z_srM.dadxus-submitted.m.-v.yna-We-were-prepared-by-the-following-granular-cleaning-agents, for the dishes of example I to IV with a volumetric weight of 1.02 kg/l:

......j,··—;· /..............J jj /// ;/IN IN KNOWS 30.0 30.0 30.0 ;27Λ 34.5 26.7 ' Carbonate 30.5 30.5 30.5 23.0 30.5 28.0 i Silica 7.4 7.4 7.4 12.0 8.0 20.3 T £ »», ' 1 ? '1 , ⁴ hPBi;y; I jm ur ₄ * ⁴ f 4.4 4.4.. 4.4 ··:''7 * ^r ' ⁵ 4.4 HÍHÍI j NaDCC, — — 2.0 — 1.5 'Inert substance' 0.75 0.75 0.75 1.9 1.2 0.5 honey7?;' , \·\; . Γ, Jíli 7 ¹ ~ 7 PAAC 1.0 1.0 — 1.0 ISlISS — -~4' 0.004 — BzP — M — »111 — ϊββΒβΐ , f»Íiř<pn 8 , í Pectinesterase : Protease 0.25 0.25' 0.25 J>FW< x — 0.01 0.01 0.01 ' 0.05 0.01 0.05 0.05 0.05 0.05 .«jitiriH· 0.1 1¾¾¾¾ ' Lipase 0.005 ifflSlllft 0.001 WW- — ; Amylase 0.003 0.001 0.01 0.02 0.01 0.01 : BTA 0.15 77|S77 0.15 — — Sulfate 23.9 23.9 23.9 31.4 17.4 and pH (1% solution) 10.8 10.8 10.8 10.7, > 10.7 12.3

Example 17

-are!adjx.&.p.laid_invention-.cleaning agents in the form of tablets weighing 25 g were prepared by -compression of granulated cleaning agent-Ra— dishes under a pressure of 13 KN/cm ² using a standard 12 hydraulic rotary press:

1 !llll|M|g|ll III — 48/8' 47.5 26.4 — — ΙΙΙΙ·8ΙΙΙ! — 26.4 14.8 25.8 0.007 lllliiB||Igl 0.05 0.03 0.075 0.01 0.005 ?6ϊ’βΒ8ββΐΛΐΙΙΒΒΐίΐ8βί — 0.01 0.005 0.001 1.6 llíliBIII··! — 6.9 11.4 1.2 IlUBSSm 1.1 4.3 ΙΙΙΙίβΙΙΙΙ! 0.8 0.7 — 0.65 — 0.4 0.5 0.2 11S8II1H1I8 — 3.2 — 25.0 14.7 3.2 10.6 10.6 11.0

Example 18

With the present invention, the following liquid dishwashing detergents I and II with a density of 1.40 kg/l were prepared:

Components ’ STPP ' Carbonate • Silica

Nonionic substance ³ Paraffin i'qňiíír^it,; .i · : ' . i

Pectinesterase * ·.-

480N* í KOH « Sulphate-./ .<

; pH (% solution)

/ ilSiíliSieiSI 33.3 20.0 2.7 ÍI88IÍ8II81! — ΪΙΙβΙΙΙΙϊ 1.1 ilB|j||ijjg|lli| 2.5 lllllllllll 2.2 ίΟΐΙΒίΐΛίϊββΙβίϊΙΙ 0.005 IjjlijMMBČlItflI 0.03 11¾¾¾¾¾¾ 0.005 0.0025 0.50 18181111118 — 6.00 1.6 lesisfieiifleiiiiss 9.1 10.0

Example 19 were-prepared—RGfollowedMckuté - cleaning 64

—α-pFséicžsRým—-invention: of solid surfaces: Folders / Pectinesterase 0.005 . Amylase 0.01 i Protease 0.05 EDTA* ___ Citrate ... 1.95 C12AS - NaC12(ethoxyph*sfran ___ . C12 dimethylamine oxide iftcs. ; ; 1.3 Hexylcarbitol'* 6.3 Water f , , . 1 up to 100%

II /// ?//in IN 0.01 0.2 0.2 0.005 0.002 0.005 .0.02 : 0.001 0.01 0.02 0.03 0.005 ÍBMB8SI 2.9 2.9' ISlBi — 2.9 JaSÍ8|j| 1.95 1.95 2.2 — 2.2 2.2 — 2.2 ___ 0.5 — 0.5 —- ΒΒβΙΐϊ 1.3 , -rA* 1.3 6.3 6.3 6.3' 6.3 100% up to 100% up to 100% up to 100%

Na ₄ ethylene diamine acetic acid

Diethylene glycol monohexyl ether

All formulations are adjusted to pH 7

Example 20 .V.sauíadu_s..pxedÍ£>i.eQím invention -hyLpaproven- spray medium for cleaning solid surfaces and removing mold occurring in the home:

Folders

Pectinesterase Amylase Protease Sodium octylsfran Sodium dodecyl sulfate Sodium hydroxide ' Silicate (Na)

PerfumeVbda/minority shares

0.01

0.01

0.01

2.0

4.0

0.8

0.04

0.35 to 100%

PATENT CLAIMS

Claims (17)

1. A cleaning composition comprising a pectin esterase substance-containing and containing other pectin enzymes. The cleaning composition according to claim 1, wherein said pectinesterase has an enzymatic effect of at least 10%, preferably 25%, more preferably 40% of its optimum effects at a pH in the range of 7 to 11. The cleaning composition of claim 2, wherein said pectinesterase has optimal effects at a pH in the range of 7 to 11. The cleaning composition according to claims 1 to 3, characterized in that it contains less than 25% by weight, preferably less than 10% by weight, more preferably less than 5% by weight. pectin esterase enzyme another pectin enzyme. Cleaning composition according to claims 1 to 4, characterized in that said pectinesterase is present at a level of from 0.0001% to 2% by weight, preferably from 0.0005% to 0.5% by weight, more preferably from 0.001% to 2% by weight. 0.1 wt. of the pure enzyme by weight of the total composition. A detergent composition according to any preceding claim, further comprising a dispersing agent. A detergent composition according to any preceding claim, further comprising another detergent enzyme. 8. A detergent composition according to claim 7 wherein said detergent enzyme is selected from the group consisting of amylase, protease, lipase, cellulase, and mixtures thereof. A cleaning composition according to any preceding claim, further comprising an enzymatic bleach system. A cleaning composition according to any preceding claim, further comprising a conventional activated bleach system with a Mn-based bleach catalyst. A cleaning composition according to any one of the preceding claims, further comprising a polymeric anti-dye composition. A detergent composition according to any one of the preceding claims, wherein said laundry detergent composition further comprises one or more ingredients selected from the group consisting of anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, saponification suppressors, suspensions. anti-dirt and anti-redeposition agents, clay smectite and the like. A cleaning composition according to any one of the preceding claims, wherein said composition is liquid, gel, in the form of bars, tablets, powder or granular. 14. A detergent composition comprising a pectin esterase substantially free of another pectin enzyme. Use of the cleaning composition according to claims 1 to 14 for washing fabrics and / or removing stains on fabrics and / or bleaching fabrics and / or softening fabrics and / or adjusting the color appearance of fabrics and / or color fastening and against coloring with one another. Use of a cleaning composition according to claims 1 to 14 for cleaning hard surfaces such as floors, walls, bathroom linings and the like. Use of the cleaning composition according to claims 1 to 14 for manual dishwashing or dishwashing